CN115729045A - Method for manufacturing laminate having conductor pattern, and transfer film - Google Patents
Method for manufacturing laminate having conductor pattern, and transfer film Download PDFInfo
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- CN115729045A CN115729045A CN202211050625.XA CN202211050625A CN115729045A CN 115729045 A CN115729045 A CN 115729045A CN 202211050625 A CN202211050625 A CN 202211050625A CN 115729045 A CN115729045 A CN 115729045A
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Abstract
The invention provides a method for manufacturing a laminate having a conductor pattern, which can manufacture a conductor pattern having a desired shape even when an anti-corrosion pattern is subjected to a cleaning treatment with an acidic solution before a plating treatment, and a transfer film. A method for manufacturing a laminate having a conductor pattern, comprising: a bonding step of bonding the transfer film to the substrate so that a surface of the transfer film on a side opposite to the temporary support comes into contact with a metal layer of the substrate having the metal layer on a surface thereof; an exposure step of pattern-exposing the photosensitive composition layer; a developing step of performing a developing treatment to form a resist pattern; a heating step of heating the resist pattern; a cleaning step of cleaning the heated resist pattern with an acidic solution; a plating step of performing plating treatment; a stripping step of stripping the resist pattern; and a removing step of removing the metal layer exposed in the peeling step and forming a conductor pattern on the substrate, wherein the photosensitive composition layer contains a thermal crosslinking agent.
Description
Technical Field
The present invention relates to a method for manufacturing a laminate having a conductor pattern and a transfer film.
Background
A method of disposing a photosensitive composition layer on an arbitrary substrate using a transfer film, exposing the photosensitive composition layer through a mask, and then developing the photosensitive composition layer is widely used because the number of steps for obtaining a predetermined pattern is small.
Patent document 1 discloses the following method: a circuit board is manufactured by laminating a photosensitive resin layer containing a predetermined component on a support, transferring the photosensitive resin layer onto a base material, forming a resist pattern by exposure and development, and then performing plating.
Patent document 1: japanese patent laid-open publication No. 2016-139154
Recently, further miniaturization of the shape of the conductor pattern is required, and the demand for shape control is further increasing.
The present inventors have found that, when the plating treatment is performed by performing a cleaning treatment with an acidic solution in order to remove the dirt of the resist pattern prior to the plating treatment by referring to the method described in patent document 1, the shape of the obtained conductor pattern is deformed from a desired shape, and thus improvement is required.
Disclosure of Invention
The present invention addresses the problem of providing a method for manufacturing a laminate having a conductor pattern, which can manufacture a conductor pattern having a desired shape even when a resist pattern is subjected to a cleaning treatment with an acidic solution prior to a plating treatment.
Another object of the present invention is to provide a transfer film.
As a result of intensive studies on the above problems, the present inventors have found that the above problems can be solved by the following configurations.
(1) A method for manufacturing a laminate having a conductor pattern, comprising the steps of:
a bonding step of bonding the transfer film having the temporary support and the negative photosensitive composition layer to the substrate so that a surface of the transfer film opposite to the temporary support contacts a metal layer of the substrate having a metal layer on a surface thereof;
an exposure step of pattern-exposing the photosensitive composition layer;
a developing step of performing a developing treatment on the exposed photosensitive composition layer to form a resist pattern;
a heating step of heating the resist pattern;
a cleaning step of cleaning the heated resist pattern with an acidic solution;
a plating step of performing plating treatment on the metal layer located in the region where the resist pattern is not arranged;
a stripping step of stripping the resist pattern; and
a removing step of removing the metal layer exposed by the peeling step to form a conductor pattern on the substrate,
a temporary support stripping step of stripping the temporary support is also provided between the bonding step and the exposure step or between the exposure step and the development step,
the photosensitive composition layer contains a thermal crosslinking agent.
(2) The method for producing a laminate having a conductor pattern according to (1), wherein,
the surface of the resist pattern heated in the heating step on the side opposite to the substrate side has an elastic modulus of 5.0GPa or more.
(3) The method for producing a laminate having a conductor pattern according to (1) or (2), wherein,
the elastic modulus of the surface of the resist pattern heated in the heating step on the side opposite to the substrate side is set as elastic modulus X,
when the elastic modulus of the resist pattern heated in the heating step is taken as the elastic modulus Y in the vicinity of the substrate side,
satisfying that X/Y is less than or equal to 1.2.
(4) The method for producing a laminate having a conductor pattern according to any one of (1) to (3),
the photosensitive composition layer contains a polymerizable compound and a polymerization initiator.
(5) The method for producing a laminate having a conductor pattern according to (4), wherein,
the polymerizable compound has an alkylene oxide-modified bisphenol structure.
(6) The method for producing a laminate having a conductor pattern according to any one of (1) to (5),
the thermal crosslinking agent contains a blocked isocyanate compound.
(7) The method for producing a laminate having a conductor pattern according to any one of (1) to (6),
the temporary support has a haze of 1.0% or less.
(8) The method for producing a laminate having a conductor pattern according to any one of (1) to (7),
the thickness of the temporary support is 50 μm or less.
(9) The method for producing a laminate having a conductor pattern according to any one of (1) to (8),
the transfer film has an intermediate layer between the temporary support and the photosensitive composition layer.
(10) The method for producing a laminate having a conductor pattern according to (9), wherein,
the middle layer is a water-soluble resin layer.
(11) The method for producing a laminate having a conductor pattern according to any one of (1) to (10),
the exposure step is a step of performing pattern exposure through a photomask.
(12) The method for producing a laminate having a conductor pattern according to any one of (1) to (10),
the exposure step is a step of pattern-exposing the photosensitive composition layer through a lens using actinic rays on which an image of the photomask is projected.
(13) The method for producing a laminate having a conductor pattern according to any one of (1) to (10),
a temporary support stripping step is provided between the bonding step and the exposure step,
the exposure step is a step of exposing the photosensitive composition layer to a pattern by bringing the surface exposed by peeling the temporary support into contact with a photomask.
(14) A transfer film having a temporary support and a negative photosensitive composition layer, wherein,
the photosensitive composition layer contains a thermal crosslinking agent,
the temporary support has a haze of 1.0% or less.
(15) The transfer film according to (14), wherein,
the thickness of the temporary support is 50 μm or less.
(16) The transfer film according to (14) or (15), wherein,
the photosensitive composition layer contains a polymerizable compound and a polymerization initiator.
(17) The transfer sheet according to (16), wherein,
the polymerizable compound has an alkylene oxide-modified bisphenol structure.
(18) The transfer film according to any one of (14) to (17), which has an intermediate layer between the temporary support and the photosensitive composition layer.
(19) The transfer film according to (18), wherein,
the middle layer is a water-soluble resin layer.
Effects of the invention
According to the present invention, it is possible to provide a method for manufacturing a laminate having a conductor pattern, which can manufacture a conductor pattern having a desired shape even when a resist pattern is subjected to a cleaning treatment with an acidic solution before a plating treatment.
Further, according to the present invention, a transfer film can be provided.
Drawings
Fig. 1 is a schematic diagram showing an example of the layer structure of the transfer film according to the embodiment.
Detailed Description
The present invention will be described in detail below.
The following description of the constituent elements may be made in accordance with a representative embodiment of the present invention, but the present invention is not limited to such an embodiment.
The meanings of the respective descriptions in the present specification are shown below.
In the present specification, the numerical range expressed by the term "to" refers to a range including numerical values before and after the term "to" as a lower limit value and an upper limit value.
In the present specification, in the numerical ranges described in stages, the upper limit value or the lower limit value described in a certain numerical range may be replaced with the upper limit value or the lower limit value described in another numerical range. In addition, in the numerical ranges described in the present specification, the upper limit value or the lower limit value described in a certain numerical range may be replaced with the values shown in the examples.
In the present specification, the term "step" includes not only an independent step but also a step that can achieve the intended purpose of the step even when it cannot be clearly distinguished from other steps.
In the present specification, "transparent" means that the average transmittance of visible light having a wavelength of 400 to 700nm is 80% or more, preferably 90% or more.
In the present specification, the average transmittance of visible light is a value measured using a spectrophotometer, and can be measured using, for example, a spectrophotometer U-3310 manufactured by Hitachi, ltd.
In the present specification, unless otherwise specified, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are values in terms of polystyrene using a standard substance, which are measured by a Gel Permeation Chromatography (GPC) analyzer using TSKgel GMHxL, TSKgel G4000HxL, or TSKgel G2000HxL (both trade names manufactured by TOSOH CORPORATION) as a column, THF (tetrahydrofuran) as an eluent, a differential refractometer as a detector, and polystyrene as a standard substance.
In the present specification, the molecular weight of the compound having a molecular weight distribution is a weight average molecular weight (Mw) unless otherwise specified.
In the present specification, unless otherwise specified, the content of the metal element is a value measured by an Inductively Coupled Plasma (ICP) spectroscopic analyzer.
In the present specification, the refractive index is a value measured at a wavelength of 550nm using an ellipsometer, unless otherwise specified.
In the present specification, unless otherwise specified, the hue is a value measured by a color difference meter (CR-221, manufactured by minolta Co., ltd.).
In the present specification, "(meth) acrylic group" is a concept including both acrylic group and methacrylic group, and "(meth) acryloyloxy group" is a concept including both acryloyloxy group and methacryloyloxy group.
In the present specification, "alkali-soluble" means that the solubility to 100g of a 1 mass% aqueous solution of sodium carbonate at 22 ℃ is 0.1g or more.
In the present specification, "water-soluble" means that the solubility of 100g of water having a pH of 7.0 at a liquid temperature of 22 ℃ is 0.1g or more. Thus, for example, a water-soluble resin refers to a resin that satisfies the solubility conditions described above.
In the present specification, "solid component" of the composition means a component forming a composition layer formed using the composition, and when the composition contains a solvent (an organic solvent, water, or the like), it means all components except the solvent. In addition, if the component is a component for forming the composition layer, the liquid component is also considered as a solid component.
The method for producing a laminate having a conductor pattern according to the present invention is characterized by including: the photosensitive composition layer contains a thermal crosslinking agent.
As a result of studies on the causes of the above problems in the prior art, the present inventors have found that the resist pattern is peeled off or decomposed when the resist pattern is washed with an acidic solution, and as a result, a conductor pattern having a desired shape cannot be obtained. Accordingly, it has been found that when a thermal crosslinking agent is contained in the photosensitive composition layer and a heat treatment is performed after the development treatment to crosslink the resist pattern, the resistance to an acidic solution is improved, and as a result, a conductor pattern having a desired shape can be obtained.
< method for producing laminate having conductor Pattern >
The method for manufacturing a laminate having a conductor pattern according to the present invention sequentially comprises:
a bonding step of bonding the transfer film to the substrate so that a surface of the transfer film, which is opposite to the temporary support, having the temporary support and the negative photosensitive composition layer is in contact with a metal layer of the substrate having the metal layer on the surface;
an exposure step of pattern-exposing the photosensitive composition layer;
a developing step of performing a developing treatment on the exposed photosensitive composition layer to form a resist pattern;
a heating step of heating the resist pattern;
a cleaning step of cleaning the heated resist pattern with an acidic solution;
a plating step of performing plating treatment on the metal layer located in the region where the resist pattern is not arranged;
a stripping step of stripping the resist pattern; and
a removing step of removing the metal layer exposed by the peeling step and forming a conductor pattern on the substrate,
a temporary support stripping step of stripping the temporary support is also provided between the bonding step and the exposure step or between the exposure step and the development step.
Hereinafter, each step will be described in detail.
[ bonding Process ]
The bonding step is a step of bonding the transfer film having the temporary support and the negative photosensitive composition layer to the substrate so that the surface of the transfer film opposite to the temporary support is in contact with the metal layer of the substrate having the metal layer on the surface.
By performing this step, a substrate with a photosensitive composition layer, which includes a substrate, a metal layer, a photosensitive composition layer, and a temporary support in this order, can be obtained.
The structure of the transfer film will be described in detail in the subsequent section.
A substrate having a metal layer on a surface thereof (a substrate with a metal layer) includes a substrate and a metal layer disposed on a surface of the substrate.
Examples of the substrate include a resin substrate, a glass substrate, a ceramic substrate, and a semiconductor substrate, and the substrate described in paragraph 0140 of international publication No. 2018/155193 is preferred.
As a material of the resin substrate, polyethylene terephthalate, cycloolefin polymer, or polyimide is preferable.
The thickness of the resin substrate is preferably 5 to 200. Mu.m, more preferably 10 to 100. Mu.m.
The metal layer is a layer containing a metal, and the metal is not particularly limited, and a known metal can be used. The metal layer is preferably a conductive layer.
Examples of the main component (so-called main metal) of the metal layer include copper, chromium, lead, nickel, gold, silver, tin, and zinc. The "main component" refers to the metal contained in the metal layer at the highest content.
The method of forming the metal layer is not particularly limited, and examples thereof include a method of coating a dispersion in which metal fine particles are dispersed and sintering the coating film, and known methods such as a sputtering method and a vapor deposition method.
The thickness of the metal layer is not particularly limited, but is preferably 50nm or more, more preferably 100nm or more. The upper limit is preferably 2 μm or less.
1 or 2 or more metal layers may be disposed on the substrate.
When 2 or more metal layers are disposed, the 2 or more metal layers may be the same or different from each other, and are preferably metal layers of different materials.
In the above bonding, it is preferable that the photosensitive composition layer side (the surface opposite to the temporary support side) of the transfer film is brought into contact with the metal layer on the substrate and pressure-bonded.
The method of pressure bonding is not particularly limited, and a known transfer method and lamination method can be used. Among them, it is preferable to overlap the surface of the photosensitive composition layer on a substrate having a metal layer, and to apply pressure and heat by a roller or the like.
For bonding, a known laminator such as a vacuum laminator and an automatic cutting laminator can be used.
The lamination temperature is not particularly limited, and is preferably 70 to 130 ℃.
[ Exposure Process ]
The exposure step is a step of pattern-exposing the photosensitive composition layer.
The "pattern exposure" is a pattern-like exposure method, and refers to exposure in which an exposed portion and an unexposed portion are present.
The positional relationship between the exposed portion (exposed region) and the unexposed portion (unexposed region) in pattern exposure can be appropriately adjusted. The exposure is preferably performed from the photosensitive composition layer side.
Examples of the exposure method in the exposure step include mask exposure, direct imaging exposure, and projection exposure, and mask exposure and projection exposure are preferable.
That is, as the exposure step, a step of performing pattern exposure through a photomask is preferable.
In addition, as the exposure step, a step of pattern-exposing the photosensitive composition layer through a lens using an actinic ray on which an image of the photomask is projected is also preferable.
When a temporary support peeling step, which will be described later, is performed between the bonding step and the exposure step, the exposure step is preferably an exposure step in which the surface exposed by peeling the temporary support is brought into contact with a photomask to perform pattern exposure. In other words, the exposure step of exposing the photosensitive composition layer in a pattern by bringing the exposed surface of the laminate from which the temporary support has been peeled away into contact with the photomask is preferable. In addition, when the transfer film has a 3-layer structure of the temporary support, the intermediate layer, and the photosensitive composition layer, the surface of the intermediate layer corresponds to the exposed surface.
By adopting such an exposure process, a higher-definition resist pattern can be obtained, and finally a higher-definition conductor pattern can be obtained.
In particular, when a temporary support peeling step described later is performed between the bonding step and the exposure step, such an exposure step is preferably employed.
In the case where a temporary support peeling step described later is performed between the exposure step and the development step, the exposure step is preferably an exposure step in which the surface of the transfer film on the side opposite to the side having the substrate in the laminate of the substrate and the transfer film obtained in the bonding step is brought into contact with a photomask to perform pattern exposure.
In the exposure step of performing pattern exposure, a curing reaction of the components contained in the photosensitive composition layer can be generated in an exposed region (region corresponding to the opening of the photomask) of the photosensitive composition layer. By performing a developing process after the exposure, the unexposed region of the photosensitive composition layer is removed to form a pattern.
The method of the present invention preferably includes a photomask removing step of removing the photomask used in the exposure step between the exposure step and the development step.
Examples of the photomask peeling step include a known peeling step.
The light source for pattern exposure may be selected and used as appropriate as long as it can irradiate light (for example, 365nm or 405 nm) in a wavelength region in which at least the photosensitive composition layer can be cured. Among them, the dominant wavelength of exposure light for pattern exposure is preferably 365nm. The dominant wavelength is a wavelength having the maximum intensity.
Examples of the light source include various lasers, light Emitting Diodes (LEDs), ultra-high pressure mercury lamps, and metal halide lamps.
The exposure amount is preferably 5 to 200mJ/cm 2 More preferably 10 to 200mJ/cm 2 。
Preferable examples of the light source, the exposure amount, and the exposure method used for the exposure are described in paragraphs [0146] to [0147] of international publication No. 2018/155193, which are incorporated herein by reference.
[ procedure for peeling off temporary support ]
The temporary support peeling step is performed between the bonding step and the exposure step or between the exposure step and the development step.
Among these, it is preferable to have a temporary support peeling step between the bonding step and the exposure step.
The temporary support peeling step is a step of peeling the temporary support from the laminate of the transfer film and the substrate with the metal layer.
Examples of the method for peeling off the temporary support include a known peeling method. Specifically, there is a cover film peeling mechanism described in paragraphs [0161] to [0162] of japanese patent application laid-open No. 2010-072589.
[ developing Process ]
The developing step is a step of forming a resist pattern by performing a developing treatment on the exposed photosensitive composition layer.
The photosensitive composition layer can be developed using a developer.
As the developer, an alkaline aqueous solution is preferable. Examples of the basic compound that can be contained in the basic aqueous solution include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, and choline (2-hydroxyethyltrimethylammonium hydroxide).
The liquid temperature of the developer in the development treatment is preferably 10 to 50 ℃, more preferably 15 to 40 ℃, and still more preferably 20 to 35 ℃.
The pH of the developer in the development treatment is preferably 9 or more, more preferably 10 or more, and further preferably 11 or more. The upper limit is preferably 14 or less, more preferably less than 13. The pH can be measured by a method in accordance with JIS Z8802-1984 using a known pH meter. The measurement temperature of pH was set to 25 ℃.
In the developer, the content of water is preferably 50% by mass or more and less than 100% by mass, and more preferably 90% by mass or more and less than 100% by mass, with respect to the total mass of the developer.
The content of the alkaline compound in the developer is preferably 0.01 to 20% by mass, more preferably 0.1 to 10% by mass, based on the total mass of the developer.
Examples of the development method include spin immersion development, shower development, spin development, and immersion development.
The developer preferably used in this specification includes, for example, the developer described in paragraph [0194] of international publication No. 2015/093271, and the developing method preferably used includes, for example, the developing method described in paragraph [0195] of international publication No. 2015/093271.
After the development and before the transfer to the next step, a rinsing process for removing the developer remaining on the substrate with the metal layer is also preferably performed. Water or the like can be used for the rinsing treatment.
After the development and/or rinsing process, a drying process may be performed to remove excess liquid from the substrate with the conductive layer.
The position and size of the resist pattern formed on the substrate with the metal layer are not particularly limited, but a thin line shape is preferable.
Specifically, the line width of the resist pattern is preferably 20 μm or less, more preferably 15 μm or less, still more preferably 10 μm or less, and particularly preferably 5 μm or less. The lower limit is usually 1.0 μm or more.
[ heating Process ]
The heating step is a step of heating the resist pattern. By performing this step, a crosslinked structure is formed in the resist pattern by a thermal crosslinking agent described later, and the resist pattern can be provided with resistance against washing with an acidic solution performed in a washing step described later.
The heating temperature is not particularly limited, but is preferably 100 to 200 ℃, more preferably 120 to 150 ℃.
The heating time is not particularly limited, but is preferably 10 to 60 minutes, more preferably 20 to 40 minutes.
The elastic modulus of the surface of the resist pattern heated in the heating step on the side opposite to the substrate side is not particularly limited, but is preferably 5.0GPa or more, more preferably 5.5GPa or more, from the viewpoint of further improving the effect of the present invention. The upper limit is not particularly limited, but 7.0GPa or less is often used.
The method of measuring the elastic modulus is as follows.
The elastic modulus was measured by Atomic Force Microscopy (AFM). The method comprises the following specific steps. The measurement is performed in the QNM mode using an atomic force microscope (e.g., AFM Dimension Icon manufactured by Bruker). As the probe, RTESPA-150 (150 KHz, 5N/m) is used, for example. The total of 5 fields of view were measured at 1 μm square for each 1 field of view, and the force curve (force curve) at 50 points was measured at 10 points for each 1 field of view, and the elastic modulus was calculated from the slope of the force curve (20% to 90% of the maximum load) in the return stroke using the Hertz contact theory. Specific examples of the correction of the AFM probe are as follows. The force curve of the quartz substrate was measured in advance, and the warpage sensitivity was calculated from the slope of the force curve. The spring constant was calculated by measuring the thermal fluctuation of the probe. For example, the spring constant was calculated by a Thermal tuning (Thermal Tune) method included in AFM software manufactured by Bruker corporation. The shape of the Tip curvature correction Sample (RM-12m.
When the elastic modulus of the surface of the resist pattern heated in the heating step on the side opposite to the substrate side is elastic modulus X, and the elastic modulus of the resist pattern heated in the heating step near the substrate side is elastic modulus Y, X/Y is not particularly limited, but is preferably 1.20 or less, more preferably 1.10 or less, from the viewpoint of further improving the effect of the present invention. The lower limit is not particularly limited, but is preferably 1.05 or more.
The method for measuring the elastic modulus X may be a method based on the Atomic Force Microscope (AFM).
The elastic modulus Y is measured as follows.
The resist pattern was cut with a slicer along the thickness direction to expose a vertical cross section of the resist pattern, and the elastic modulus at any one of height positions of 0 to 20% from the substrate with respect to the entire thickness of the resist pattern in the vertical cross section was measured by the same method as the elastic modulus X, and this was defined as the elastic modulus Y. That is, the vicinity of the substrate side of the resist pattern refers to a range of a height position from the substrate to the entire thickness of the resist pattern in a vertical cross section of the resist pattern, the height position being 0 to 20%.
[ cleaning Process ]
The cleaning step is a step of cleaning the resist pattern heated in the heating step with an acidic solution.
The acidic solution is not particularly limited as long as it is a solution containing an acid.
Examples of the acid in the acidic solution include sulfuric acid, nitric acid, hydrogen chloride, phosphoric acid, hydrofluoric acid, sulfamic acid, and oxalic acid.
The concentration of the acid in the acidic solution is not particularly limited, but the concentration of the acid component is preferably 5 to 30% by mass, more preferably 10 to 20% by mass, based on the total mass of the acidic solution.
The acidic solution contains a solvent in advance.
Examples of the solvent include water and an organic solvent.
Examples of the organic solvent include alcohol solvents, ester solvents, ketone solvents, amide solvents, and hydrocarbon solvents.
The method of washing the resist pattern with the acidic solution is not particularly limited as long as the resist pattern can be brought into contact with the acidic solution. For example, a method of supplying an acidic solution onto the resist pattern and a method of immersing the resist pattern in an acidic solution may be mentioned.
The contact time of the resist pattern with the acidic solution is not particularly limited, but is preferably 1 to 20 minutes, more preferably 3 to 10 minutes.
The liquid temperature of the acidic solution when the resist pattern is brought into contact with the acidic solution is preferably 25 to 50 ℃, more preferably 30 to 40 ℃.
[ plating Process ]
The plating step is a step of plating the metal layer located in the region where the resist pattern is not arranged.
By performing this step, a plating layer can be formed on the metal layer located in the region where the resist pattern is not arranged.
Examples of the plating method include an electrolytic plating method and an electroless plating method, and the electrolytic plating method is preferred from the viewpoint of productivity.
When the plating step is performed, a plating layer having the same pattern shape as the region where the resist pattern is not arranged (the opening of the resist pattern) can be obtained on the substrate with the metal layer.
Examples of the metal contained in the plating layer include known metals.
Specifically, metals such as copper, chromium, lead, nickel, gold, silver, tin, and zinc, and alloys of these metals can be mentioned.
Among them, the plating layer preferably contains copper or an alloy thereof from the viewpoint of more excellent conductivity of the conductor pattern. Further, the plating layer preferably contains copper as a main component from the viewpoint of more excellent conductivity of the conductor pattern.
The thickness of the plating layer is preferably 0.1 μm or more, more preferably 1 μm or more. The upper limit is preferably 20 μm or less.
[ peeling Process ]
The stripping step is a step of stripping the resist pattern.
The method of stripping the residual resist pattern is not particularly limited, and a method of removing by chemical treatment may be mentioned, and a method of removing using a stripping solution is preferred.
The removal may be performed by a known method such as spray coating, shower coating, spin coating, or the like using a stripping liquid.
Examples of the stripping solution include a solution obtained by dissolving an inorganic base component or an organic base component in water, dimethyl sulfoxide, N-methylpyrrolidone, or a mixed solution thereof. Examples of the inorganic alkali component include sodium hydroxide and potassium hydroxide. Examples of the organic base component include a primary amine compound, a secondary amine compound, a tertiary amine compound, and a quaternary ammonium salt compound. As the basic organic compound, tetramethylammonium hydroxide or an alkanolamine compound is preferable. The stripping liquid also preferably does not dissolve the conductive layer.
As a method for peeling off the resist pattern, a method of immersing the substrate having the residual resist pattern in a peeling liquid under stirring at a liquid temperature of preferably 30 to 80 ℃, more preferably 50 to 80 ℃ for 1 to 30 minutes can be mentioned.
The pH of the stripping solution in the stripping treatment is preferably 11 or more, more preferably 12 or more, and still more preferably 13 or more. The upper limit is preferably 14 or less, more preferably 13.8 or less. The pH can be measured by a method in accordance with JIS Z8802-1984 using a known pH meter. The measurement temperature of pH was set to 25 ℃.
The liquid temperature of the stripping liquid when the stripping treatment is performed is preferably higher than the liquid temperature of the developing liquid when the developing treatment is performed. Specifically, the value obtained by subtracting the liquid temperature of the developing solution from the liquid temperature of the stripping solution (the liquid temperature of the stripping solution — the liquid temperature of the developing solution) is preferably 10 ℃ or higher, and more preferably 20 ℃ or higher. The upper limit is preferably 100 ℃ or lower, more preferably 80 ℃ or lower.
The pH of the stripping solution when the stripping treatment is performed is preferably higher than the pH of the developing solution when the developing treatment is performed. Specifically, the value obtained by subtracting the pH of the developing solution from the pH of the stripping solution (the pH of the stripping solution — the pH of the developing solution) is preferably 1 or more, and more preferably 1.5 or more. The upper limit is preferably 5 or less, more preferably 4 or less.
It is also preferable to perform a rinsing process for removing the stripping liquid remaining on the substrate after the resist pattern is stripped with the stripping liquid. Water or the like can be used for the rinsing treatment.
After the stripping and/or rinsing treatment of the resist pattern by the stripping liquid, a drying treatment for removing an excess liquid from the substrate may be performed.
[ removal Process ]
The removing step is a step of removing the metal layer exposed in the peeling step and forming a conductor pattern on the substrate.
In the removal step, etching treatment of the metal layer located in the non-pattern-formed region (in other words, the region not protected by the plating layer) is performed using the plating layer formed in the plating step as an etching resist.
The method for removing a part of the metal layer is not particularly limited, and a known etching solution is preferably used.
Examples of known etching solutions include ferric chloride solution, cupric chloride solution, ammonia-soda solution, sulfuric acid-hydrogen peroxide mixed solution, phosphoric acid-hydrogen peroxide mixed solution, and the like.
When the removing step is performed, the metal layer exposed on the surface is removed from the substrate, and the plating layer (conductor pattern) having the pattern shape remains, so that a laminate having the conductor pattern can be obtained.
The upper limit of the line width of the conductor pattern to be formed is preferably 8 μm or less, and more preferably 6 μm or less. The lower limit is not particularly limited, but is often 1 μm or more.
[ other Processes ]
The method for producing the laminate having the conductor pattern may include any process (other process) other than the above-described process.
Examples of the step include, but are not limited to, the step of reducing the visible light reflectance described in paragraph [0172] of international publication No. 2019/022089, and the step of forming a new metal layer on the insulating film described in paragraph [0172] of international publication No. 2019/022089.
A step of reducing the reflectance of visible rays
The method for producing a laminate having a conductor pattern may include a step of performing a treatment for reducing the visible light reflectance of part or all of the plurality of metal layers of the base material.
As the treatment for reducing the visible light reflectance, an oxidation treatment may be mentioned. When the base material has a metal layer containing copper, the visible light reflectance of the metal layer can be reduced by oxidizing copper to form copper oxide and blackening the metal layer.
The treatment for reducing the reflectance of visible light is described in paragraphs [0017] to [0025] of Japanese patent application laid-open No. 2014-150118 and paragraphs [0041], [0042], [0048] and [0058] of Japanese patent application laid-open No. 2013-206315, and the contents of these publications are incorporated in the present specification.
A step of forming an insulating film, a step of forming a new metal layer on the surface of the insulating film-
The method for producing a laminate having a conductor pattern preferably includes a step of forming an insulating film on the surface of the circuit wiring and a step of forming a new metal layer on the surface of the insulating film.
Through the above steps, the second electrode pattern insulated from the first electrode pattern can be formed.
The step of forming the insulating film is not particularly limited, and a known method of forming a permanent film may be used. Further, an insulating film having a desired pattern may be formed by photolithography using a photosensitive material having an insulating property.
In the method for manufacturing a laminate having a conductor pattern, it is also preferable to use a substrate having a plurality of metal layers on both surfaces of a base material, and to form a circuit successively or simultaneously with respect to the metal layers formed on both surfaces of the base material. With this configuration, it is possible to form a circuit wiring for a touch panel in which a first conductor pattern is formed on one surface of a base material and a second conductor pattern is formed on the other surface. Further, it is also preferable that the circuit wiring for a touch panel having such a configuration is formed from both surfaces of the base material in a roll-to-roll manner.
< use of laminate having conductor Pattern >
The method for manufacturing a laminate having a conductor pattern can be applied to the manufacture of conductive films such as touch panels, transparent heaters, transparent antennas, electromagnetic shielding materials, and light control films; manufacturing a printed circuit board and a semiconductor package; manufacturing a column and a pin for interconnection between semiconductor chips or packages; manufacturing a metal mask; and manufacturing Tape substrates such as COF (Chip on Film) and TAB (Tape Automated Bonding).
The touch panel may be a capacitive touch panel. The method for manufacturing a laminate according to the present invention can be used for forming a conductive film or a peripheral circuit wiring in a touch panel. The touch panel can be applied to, for example, a display device such as an organic EL (electro-luminescence) display device or a liquid crystal display device.
< transfer film >
The transfer film used in the method for manufacturing a laminate having a conductor pattern of the present invention has a temporary support and a negative photosensitive composition layer, and the photosensitive composition layer contains a thermal crosslinking agent.
The transfer film may have other layers besides the temporary support and the photosensitive composition layer.
Examples of the other layer include an intermediate layer described later. The transfer film may have other members (e.g., a protective film) described later.
As an embodiment of the transfer film, for example, the following configuration (1) or (2) can be given, and the configuration (2) is preferable.
(1) "temporary support/photosensitive composition layer/protective film"
(2) "temporary support/intermediate layer/photosensitive composition layer/protective film"
The transfer film preferably has an intermediate layer.
From the viewpoint of suppressing the generation of bubbles in the bonding step, the maximum width of the waviness of the transfer film is preferably 300 μm or less, more preferably 200 μm or less, and further preferably 60 μm or less. The lower limit of the maximum width of the corrugations is 0 μm or more, preferably 0.1 μm or more, and more preferably 1 μm or more.
The maximum width of the moire of the transfer film is a value measured by the following procedure.
First, the transfer film was cut into a size of 20cm long × 20cm wide in a direction perpendicular to the main surface to prepare a test sample. In addition, when the transfer film has a protective film, the protective film is peeled off. Next, the test sample was allowed to stand on a table having a smooth and horizontal surface so that the surface of the temporary support and the table were opposed to each other. After standing, the surface of the test sample is scanned by a laser microscope (for example, VK-9700SP manufactured by KEYENCE CORPORATION) over a range of 10cm square from the center of the test sample to obtain a three-dimensional surface image, and the minimum concave height is subtracted from the maximum convex height observed in the obtained three-dimensional surface image. The above operation was performed on 10 test samples, and the arithmetic average value thereof was defined as "maximum width of moire of transfer film".
When another composition layer is further provided on the surface of the photosensitive composition layer opposite to the temporary support in the photosensitive composition layer of the transfer film, the total thickness of the other composition layers is preferably 0.1 to 30%, more preferably 0.1 to 20%, based on the total thickness of the photosensitive composition layers.
From the viewpoint of more excellent adhesion, the transmittance of light having a wavelength of 365nm of the photosensitive composition layer is preferably 10% or more, more preferably 30% or more, and further preferably 50% or more. The upper limit is preferably 99.9% or less, more preferably 99.0% or less.
An example of an embodiment of the transfer film will be described.
The transfer film 10 shown in fig. 1 includes a temporary support 11, a composition layer 17 including an intermediate layer 13 and a photosensitive composition layer 15, and a protective film 19 in this order.
The transfer film 10 shown in fig. 1 has the intermediate layer 13 and the protective film 19, but may not have the intermediate layer 13 and the protective film 19.
In fig. 1, each layer (for example, a photosensitive composition layer, an intermediate layer, and the like) other than the protective film 19 which can be disposed on the temporary support 11 is also referred to as a "composition layer".
Hereinafter, the transfer film will be described in detail with respect to each member and each component.
[ temporary support ]
The transfer film has a temporary support.
The temporary support is a member for supporting the photosensitive composition layer, and is finally removed by a peeling treatment.
The temporary support may have a single-layer structure or a multi-layer structure.
The temporary support is preferably a film, and more preferably a resin film. Further, as the temporary support, a film which is flexible and does not undergo significant deformation, shrinkage, or elongation under pressure or under pressure and heat, and a film which is free from deformation such as wrinkles or scratches is also preferable.
Examples of the film include a polyethylene terephthalate film (e.g., a biaxially stretched polyethylene terephthalate film), a polymethyl methacrylate film, a cellulose triacetate film, a polystyrene film, a polyimide film, and a polycarbonate film, and a polyethylene terephthalate film is preferable.
From the viewpoint of enabling pattern exposure via the temporary support, the temporary support preferably has high transparency, and the transmittance at 365nm is preferably 60% or more, more preferably 70% or more.
From the viewpoint of pattern formability during pattern exposure via the temporary support and transparency of the temporary support, the temporary support preferably has a low haze. Specifically, the value of the haze of the temporary support is preferably 2.0% or less, more preferably 1.0% or less, and further preferably 0.5% or less. The lower limit is not particularly limited, and may be 0.1% or more.
From the viewpoint of pattern formability during pattern exposure via the temporary support and transparency of the temporary support, the number of fine particles, foreign substances, and defects contained in the temporary support is preferably small. The number of particles, foreign matters and defects having a diameter of 1 μm or more in the temporary support is preferably 50/10 mm 2 The number of cells per 10mm is preferably 10 or less 2 Hereinafter, more preferably 3/10 mm 2 Hereinafter, particularly preferably 0 piece/10 mm 2 。
The thickness of the temporary support is more preferably 5 μm or more. The upper limit is preferably 200 μm or less, more preferably 150 μm or less, further preferably 50 μm or less, particularly preferably 20 μm or less, and most preferably 16 μm or less, from the viewpoint of ease of handling and versatility.
The thickness of the temporary support was calculated as an average value of arbitrary 5 points measured by cross-sectional observation based on SEM (Scanning Electron microscope).
The temporary support may have a layer containing fine particles (lubricant layer) on one surface or both surfaces of the temporary support from the viewpoint of handling properties.
The diameter of the fine particles contained in the lubricant layer is preferably 0.05 to 0.8 μm.
The thickness of the lubricant layer is preferably 0.05 to 1.0. Mu.m.
From the viewpoint of improving the adhesion between the temporary support and the photosensitive composition layer, the surface of the temporary support that is in contact with the photosensitive composition layer may be subjected to a surface modification treatment.
Examples of the surface modification treatment include treatments using UV irradiation, corona discharge, plasma, and the like.
The exposure amount in UV irradiation is preferably 10 to 2000mJ/cm 2 More preferably 50 to 1000mJ/cm 2 。
If the exposure amount is within the above range, the lamp output and the illuminance are not particularly limited.
Examples of the light source for UV irradiation include a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a carbon arc lamp, a metal halide lamp, a xenon lamp, a chemical lamp, an electrodeless discharge lamp, and a Light Emitting Diode (LED) that emit light in a wavelength band of 150 to 450 nm.
Examples of the temporary support include a biaxially stretched polyethylene terephthalate film having a thickness of 16 μm, a biaxially stretched polyethylene terephthalate film having a thickness of 12 μm, and a biaxially stretched polyethylene terephthalate film having a thickness of 9 μm.
Examples of the temporary support include paragraphs [0017] to [0018] of Japanese patent application laid-open No. 2014-085643, paragraphs [0019] to [0026] of Japanese patent application laid-open No. 2016-027363, paragraphs [0041] to [0057] of International publication No. 2012/081680, and paragraphs [0029] to [0040] of International publication No. 2018/179370, which are incorporated herein by reference.
Examples of commercially available temporary supports include registered trademarks lumiror 16KS40 and lumiror 16FB40 (both manufactured by tomayndustries, inc.); cosmoshine a4100, cosmoshine a4300, and Cosmoshine a8300 (manufactured by Toyobo co.
[ photosensitive composition layer ]
The transfer film has a negative photosensitive composition layer.
Hereinafter, the respective components contained in the photosensitive composition layer will be described in order. The following description will be made of a thermal crosslinking agent which is one of the characteristic points of the present invention.
(thermal crosslinking agent)
The photosensitive composition layer contains a thermal crosslinking agent.
Examples of the thermal crosslinking agent include methylol compounds and blocked isocyanate compounds. Among them, blocked isocyanate compounds are preferable from the viewpoint of the strength of the obtained cured film and the adhesiveness of the obtained uncured film.
Since the blocked isocyanate compound reacts with a hydroxyl group and a carboxyl group, for example, when a resin and/or a polymerizable compound has at least one of a hydroxyl group and a carboxyl group, the hydrophilicity of the formed film is reduced, and the function tends to be enhanced when the film obtained by curing the negative photosensitive composition layer is used as a protective film.
The blocked isocyanate compound is a "compound having a structure in which an isocyanate group of an isocyanate is protected (so-called mask) with a blocking agent".
The dissociation temperature of the blocked isocyanate compound is not particularly limited, but is preferably 100 to 160 ℃, more preferably 130 to 150 ℃.
The dissociation temperature of the blocked isocyanate means "a temperature of an endothermic peak accompanying deprotection reaction of the blocked isocyanate when measured by DSC (Differential scanning calorimetry) analysis using a Differential scanning calorimeter".
As the differential scanning calorimeter, for example, a differential scanning calorimeter (model: DSC 6200) manufactured by Seiko Instruments Inc. can be preferably used. However, the differential scanning calorimeter is not limited thereto.
Examples of the blocking agent having a dissociation temperature of 100 to 160 ℃ include an active methylene compound [ malonic diester (dimethyl malonate, diethyl malonate, di-N-butyl malonate, di-2-ethylhexyl malonate, etc.) ], an oxime compound (a compound having a structure represented by-C (= N-OH) -in a molecule, such as formaldoxime, acetaldoxime, acetoxime, methylethylketoxime, and cyclohexanone oxime).
Among these, the blocking agent having a dissociation temperature of 100 to 160 ℃ is preferably at least one selected from oxime compounds, for example, from the viewpoint of storage stability.
For example, the blocked isocyanate compound preferably has an isocyanurate structure from the viewpoints of improving the brittleness of the film, improving the adhesion to the transfer target, and the like.
The blocked isocyanate compound having an isocyanurate structure can be obtained, for example, by isocyanurating hexamethylene diisocyanate to protect it.
Among blocked isocyanate compounds having an isocyanurate structure, compounds having an oxime structure using an oxime compound as a blocking agent are preferable from the viewpoint that the dissociation temperature is more easily set in a preferable range and the development residue is easily reduced than those of compounds having no oxime structure.
The blocked isocyanate compound may have a polymerizable group.
The polymerizable group is not particularly limited, and a known polymerizable group can be used, and a radical polymerizable group is preferred.
Examples of the polymerizable group include an ethylenically unsaturated group such as a (meth) acryloyloxy group, a (meth) acrylamide group, and a styryl group, and a group having an epoxy group such as a glycidyl group.
Among these, the polymerizable group is preferably an ethylenically unsaturated group, more preferably a (meth) acryloyloxy group, and still more preferably an acryloyloxy group.
As the blocked isocyanate compound, commercially available products can be used.
Examples of commercially available products of the blocked isocyanate compound include Karenz (registered trademark) AOI-BM, karenz (registered trademark) MOI-BP, and the like (manufactured by SHOWA DENKO K., supra), and capped Duranate series (for example, duranate TPA-B80E, duranate WT32-B75P, and Duranate SBB-70P, and the like, manufactured by ASI KASEI CORATION).
Further, as the blocked isocyanate compound, a compound having the following structure can be used.
[ chemical formula 1]
The thermal crosslinking agent may be used alone or in combination of two or more.
The content of the thermal crosslinking agent in the photosensitive composition layer is preferably 0.01 to 10% by mass, and more preferably 0.1 to 5% by mass, based on the total mass of the photosensitive composition layer.
(resin)
The photosensitive composition layer may contain a resin.
The resin included in the photosensitive composition layer may be resin a which is an alkali-soluble resin.
The acid value of the resin a is preferably 220mgKOH/g or less, more preferably less than 200mgKOH/g, and even more preferably less than 190mgKOH/g, from the viewpoint of suppressing swelling of the negative photosensitive composition layer by the developer to further improve the resolution.
The lower limit of the acid value of the resin A is not particularly limited, but from the viewpoint of more excellent developability, the lower limit is more preferably 120mgKOH/g or more, still more preferably 150mgKOH/g or more, and particularly preferably 170mgKOH/g or more.
The acid value (mgKOH/g) was the mass [ mg ] of potassium hydroxide required to neutralize 1g of the sample. The acid value can be calculated from the average content of acid groups in the compound, for example. The acid value of the resin a may be adjusted by the kind of the structural unit constituting the resin a and the content of the structural unit containing an acid group described later.
The weight average molecular weight of the resin A is not particularly limited, and is preferably 5,000 to 500,000. When the weight average molecular weight is 500,000 or less, it is preferable from the viewpoint of improving the resolution and the developability. The weight average molecular weight is more preferably 100,000 or less, and still more preferably 60,000 or less. On the other hand, when the weight average molecular weight is 5,000 or more, it is preferable from the viewpoint of controlling the properties of the developed aggregates and the properties of the unexposed film such as the edge meltability and the chipping property in the case of using the negative photosensitive resin laminate. The weight average molecular weight is more preferably 10,000 or more, still more preferably 20,000 or more, and particularly preferably 30,000 or more.
The edge meltability means how easily the negative photosensitive composition layer overflows from the end face of the roll when the transfer film is wound into a roll as a negative photosensitive resin laminate. The swarf property is the ease with which swarf can be scattered when the unexposed film is cut with a cutter. If the chips adhere to the upper surface of the negative photosensitive resin laminate, they are transferred to a mask in a subsequent exposure step or the like, resulting in a defective product.
The degree of dispersion of the resin A is preferably 1.0 to 6.0, more preferably 1.0 to 5.0, still more preferably 1.0 to 4.0, and particularly preferably 1.0 to 3.0. In the present invention, the degree of dispersion is the ratio of the weight average molecular weight to the number average molecular weight (weight average molecular weight/number average molecular weight).
In the present invention, the weight average molecular weight and the number average molecular weight are values measured by gel permeation chromatography.
The glass transition temperature Tg of the resin A is preferably from 30 to 135 ℃. By using the resin a having a Tg of 135 ℃ or less, it is possible to suppress deterioration in the line width or resolution when the focus position is shifted during exposure. From this viewpoint, the Tg of the alkali-soluble polymer is more preferably 130 ℃ or lower, still more preferably 120 ℃ or lower, and particularly preferably 110 ℃ or lower. From the viewpoint of improving the edge melting resistance, it is preferable to use the resin a having a Tg of 30 ℃. From this viewpoint, the Tg of the resin A is more preferably 40 ℃ or higher, still more preferably 50 ℃ or higher, particularly preferably 60 ℃ or higher, and most preferably 70 ℃ or higher.
Structural units derived from monomers having aromatic hydrocarbon groups
In addition, the resin a preferably contains a structural unit derived from a monomer having an aromatic hydrocarbon group, from the viewpoint of suppressing deterioration in the line width or resolution when the focus position shifts during exposure. Examples of the aromatic hydrocarbon group include a substituted or unsubstituted phenyl group and a substituted or unsubstituted aralkyl group.
The content of the structural unit derived from the monomer having an aromatic hydrocarbon group in the resin a is preferably 20 mass% or more, and more preferably 30 mass% or more, with respect to all the structural units of the resin a. The upper limit is not particularly limited, but is preferably 95% by mass or less, and more preferably 85% by mass or less. In addition, when a plurality of resins a are contained, it is preferable that the average value of the contents of the structural units derived from the monomer having an aromatic hydrocarbon group is within the above range.
Examples of the monomer having an aromatic hydrocarbon group include a monomer having an aralkyl group, styrene, and a polymerizable styrene derivative (for example, methylstyrene, vinyltoluene, tert-butoxystyrene, acetoxystyrene, styrene dimer, styrene trimer, and the like). Among them, monomers having an aralkyl group or styrene are preferable.
When the monomer having an aromatic hydrocarbon group is styrene, the content of the structural unit derived from styrene is preferably 10 to 70% by mass, more preferably 15 to 65% by mass, further preferably 20 to 60% by mass, and particularly preferably 25 to 55% by mass, based on all the structural units of the resin a. When the photosensitive composition layer contains a plurality of alkali-soluble polymers, the content of the structural unit derived from the monomer having an aromatic hydrocarbon group is determined as a weight average value.
Examples of the aralkyl group include a phenylalkyl group which may have a substituent, and a benzyl group which may have a substituent is preferable.
Examples of the monomer containing a phenylalkyl group which may have a substituent include phenylethyl (meth) acrylate and the like.
Examples of the monomer containing a benzyl group which may have a substituent include (meth) acrylates having a benzyl group such as benzyl (meth) acrylate and chlorobenzyl (meth) acrylate; the vinyl monomer having a benzyl group such as vinylbenzyl chloride or vinylbenzyl alcohol is preferably a (meth) acrylate having a benzyl group, and more preferably benzyl (meth) acrylate.
When the monomer having an aromatic hydrocarbon group is benzyl (meth) acrylate, the content of the structural unit derived from benzyl (meth) acrylate is preferably 10 to 90% by mass, more preferably 15 to 85% by mass, based on all the structural units of the resin a.
Structural units derived from monomers having carboxyl groups-
The resin a may have a structural unit derived from a monomer having a carboxyl group.
Examples of the monomer having a carboxyl group include (meth) acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, 4-vinylbenzoic acid, maleic anhydride, and maleic acid half ester. Among these, (meth) acrylic acid is preferable.
The content of the structural unit derived from the monomer having a carboxyl group in the resin a is preferably 5 to 50% by mass, more preferably 10 to 40% by mass, and further preferably 15 to 30% by mass, based on all the structural units of the resin a.
From the viewpoint of developing a good developability, from the viewpoint of controlling the edge meltability, and the like, the content is preferably 5% by mass or more. From the viewpoint of high resolution and curl shape of the resist pattern, and further from the viewpoint of chemical resistance of the resist pattern, the content is preferably 50 mass% or less.
-non-acidic structural units-
The resin a may contain a non-acidic structural unit derived from a monomer which is non-acidic and has at least 1 polymerizable unsaturated group in the molecule.
Examples of the monomer (non-acidic monomer) include (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, cyclohexyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate; vinyl alcohol esters such as vinyl acetate; and (meth) acrylonitrile, and the like. Among them, methyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, or n-butyl (meth) acrylate is preferable, and methyl (meth) acrylate is more preferable.
The content of the structural unit derived from a non-acidic monomer in the resin a is preferably 1 to 60% by mass, more preferably 2 to 50% by mass, and still more preferably 2 to 40% by mass, based on all the structural units of the resin a.
The resin a may have any of a linear structure, a branched structure, and an alicyclic structure in a side chain.
In the present specification, "main chain" represents a relatively longest bonding chain in a molecule of a polymer compound constituting a resin, and "side chain" represents a group of atoms branched from the main chain.
By using a monomer containing a group having a branch structure in a side chain or a monomer containing a group having an alicyclic structure in a side chain, the branch structure or the alicyclic structure can be introduced into the side chain of the alkali-soluble polymer. The group having an alicyclic structure may be monocyclic or polycyclic.
Specific examples of the monomer containing a group having a branched structure in a side chain include isopropyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, isoamyl (meth) acrylate, tert-amyl (meth) acrylate, sec-amyl (meth) acrylate, 2-octyl (meth) acrylate, 3-octyl (meth) acrylate, and tert-octyl (meth) acrylate. Among these, isopropyl (meth) acrylate, isobutyl (meth) acrylate, or tert-butyl methacrylate is preferable, and isopropyl methacrylate or tert-butyl methacrylate is more preferable.
Specific examples of the monomer containing a group having an alicyclic structure in a side chain include a monomer having a monocyclic aliphatic hydrocarbon group and a monomer having a polycyclic aliphatic hydrocarbon group. Further, a (meth) acrylate having an alicyclic hydrocarbon group having 5 to 20 carbon atoms can be mentioned. More specific examples thereof include (bicyclo [2.2.1] heptyl-2) acrylate, (meth) acrylic acid 1-adamantyl ester, (meth) acrylic acid 2-adamantyl ester, (meth) acrylic acid 3-methyl-1-adamantyl ester, (meth) acrylic acid 3, 5-dimethyl-1-adamantyl ester, (meth) acrylic acid 3-ethyl adamantyl ester, (meth) acrylic acid 3-methyl-5-ethyl-1-adamantyl ester, (meth) acrylic acid 3,5, 8-triethyl-1-adamantyl ester, (meth) acrylic acid 3, 5-dimethyl-8-ethyl-1-adamantyl ester, (meth) acrylic acid 2-methyl-2-adamantyl ester, (meth) acrylic acid 2-ethyl-2-adamantyl ester, (meth) acrylic acid 3-hydroxy-1-adamantyl ester, (meth) acrylic acid octahydro-4, 7-methylindene (methaonden) -5-yl ester, (meth) acrylic acid octahydro-4, 7-methylindene-1-yl methyl ester, (meth) acrylic acid tricyclo-menthyl ester, 3-hydroxy-2, 6-trimethyl-bicyclo [3.1.1] heptyl (meth) acrylate, 3, 7-trimethyl-4-hydroxy-bicyclo [4.1.0] heptyl (meth) acrylate, norbornyl (meth) acrylate, isobornyl (meth) acrylate, fenchyl (meth) acrylate, 2, 5-trimethylcyclohexyl (meth) acrylate, cyclohexyl (meth) acrylate, and the like. Among these (meth) acrylates, preferred is cyclohexyl (meth) acrylate, (norbornyl (meth) acrylate, isobornyl (meth) acrylate, 1-adamantyl (meth) acrylate, 2-adamantyl (meth) acrylate, fenchyl (meth) acrylate, 1-menthyl (meth) acrylate, or tricyclodecane (meth) acrylate, and more preferred is cyclohexyl (meth) acrylate, (norbornyl (meth) acrylate, isobornyl (meth) acrylate, 2-adamantyl (meth) acrylate, or tricyclodecane (meth) acrylate.
Structural units having polymerizable groups-
The resin a may have a polymerizable group, or may contain a structural unit having a polymerizable group.
The polymerizable group is preferably a radical polymerizable group, and more preferably an ethylenically unsaturated group. Also, when the resin a has an ethylenically unsaturated group, the resin a preferably contains a structural unit having an ethylenically unsaturated group in a side chain.
As the ethylenically unsaturated group, an allyl group or a (meth) acryloyloxy group is more preferable.
The structural unit having a polymerizable group is preferably a structural unit represented by the formula (P).
[ chemical formula 2]
In the formula (P), R P Represents a hydrogen atom or a methyl group. L is P Represents a 2-valent linking group. P represents a polymerizable group.
R P Represents a hydrogen atom or a methyl group.
As R P Preferably a hydrogen atom.
L P Represents a 2-valent linking group.
As the above-mentioned linking group having a valence of 2, examples thereof include-CO-, -O-,; -S-, -SO 2 -、-NR N A 2-valent hydrocarbon group, and a 2-valent group formed by combining these. R is N Represents a substituent.
Examples of the hydrocarbon group include an alkylene group, a cycloalkylene group, and an arylene group.
The alkylene group may be linear or branched. The alkylene group preferably has 1 to 10 carbon atoms, more preferably 2 to 8 carbon atoms, and still more preferably 3 to 5 carbon atoms. The above alkylene group may have a hetero atom, and a methylene group in the above alkylene group may be substituted with a hetero atom. The hetero atom is preferably an oxygen atom, a sulfur atom or a nitrogen atom, and more preferably an oxygen atom.
The cycloalkylene group may be any of a monocyclic ring and a polycyclic ring. The carbon number of the cycloalkylene group is preferably 3 to 20, more preferably 5 to 10, and still more preferably 6 to 8.
The arylene group may be a single ring or a polycyclic ring. The arylene group preferably has 6 to 20, more preferably 6 to 15, and still more preferably 6 to 10 carbon atoms. As the above arylene group, phenylene group is preferable.
The cycloalkylene group and the arylene group may have a hetero atom as a ring member atom. The heteroatom is preferably an oxygen atom, a sulfur atom or a nitrogen atom, and more preferably an oxygen atom.
The above hydrocarbon group may have a substituent.
Examples of the substituent include a halogen atom (e.g., fluorine atom), a hydroxyl group, a nitro group, a cyano group, an alkyl group, an alkoxy group, an alkoxycarbonyl group, and an alkenyl group, and a hydroxyl group is preferable.
As L P An alkylene group which may have a hetero atom is preferable.
P represents a polymerizable group.
The polymerizable group is as described above.
Examples of the structural unit having a polymerizable group include, but are not limited to, the structural units described below.
[ chemical formula 3]
In the above structural units, rx represents a hydrogen atom or a methyl group. In the above structural units, ry represents a hydrogen atom or a methyl group.
The resin a may contain one kind of structural unit having a polymerizable group alone, or may contain two or more kinds.
When the resin a contains a structural unit having a polymerizable group, the content of the structural unit having a polymerizable group is preferably 5 to 70% by mass, more preferably 10 to 50% by mass, and further preferably 20 to 40% by mass, based on all the structural units of the resin a, from the viewpoint that the effect of the present invention is more excellent.
From the viewpoint of further improving the effect of the present invention, the content of the structural unit having a polymerizable group in the resin a is preferably 5 to 70 mol%, more preferably 10 to 60 mol%, and still more preferably 20 to 50 mol% based on all the structural units of the resin a.
Examples of the method for introducing a polymerizable group into the resin a include the following methods: compounds such as epoxy compounds, blocked isocyanate compounds, vinyl sulfone compounds, aldehyde compounds, methylol compounds and carboxylic anhydride compounds are reacted with functional groups such as hydroxyl group, carboxyl group, primary amino group, secondary amino group, acetoacetyl group (acetoacetyl group) and sulfo group.
Preferred examples of the method for introducing a polymerizable group into the resin a include the following methods: after a polymer having a carboxyl group is synthesized by a polymerization reaction, (meth) acryloyloxy group is introduced into the polymer by reacting a (meth) acrylate having an epoxy group such as glycidyl (meth) acrylate with a part of the carboxyl group of the obtained polymer by a high molecular reaction. Another method includes the following steps: after a polymer having a hydroxyl group is synthesized by a polymerization reaction, (meth) acryloyloxy group is introduced into the polymer by reacting a (meth) acrylate having an isocyanate group with a part of the hydroxyl group of the obtained polymer by a high molecular reaction.
By this method, a resin a having a (meth) acryloyloxy group in a side chain can be obtained.
The polymerization reaction is preferably carried out at a temperature of 70 to 100 ℃ and more preferably at a temperature of 80 to 90 ℃. As the polymerization initiator used for the above polymerization reaction, an azo-based initiator is preferable, and for example, V-601 (trade name) or V-65 (trade name) manufactured by FUJIFILM Wako Pure Chemical Corporation is more preferable. The polymerization reaction is preferably carried out at a temperature of 80 to 110 ℃. In the above-mentioned polymer reaction, a catalyst such as ammonium salt is preferably used.
One kind of the resin A may be used alone, or two or more kinds may be used.
When two or more kinds are used, it is preferable to use two kinds of the resin a containing a structural unit derived from a monomer having an aromatic hydrocarbon group in a mixed manner or to use the resin a containing a structural unit derived from a monomer having an aromatic hydrocarbon group in a mixed manner and the resin a not containing a structural unit derived from a monomer having an aromatic hydrocarbon group in a mixed manner. In the latter case, the proportion of the resin a containing a structural unit derived from a monomer having an aromatic hydrocarbon group is preferably 50% by mass or more, more preferably 70% by mass or more, further preferably 80% by mass or more, and particularly preferably 90% by mass or more, based on the total mass of the resin a.
The resin a can be synthesized by polymerizing the above-mentioned single or plural monomers using a radical polymerization initiator such as a peroxide polymerization initiator (e.g., benzoyl peroxide) and an azo polymerization initiator (e.g., azobisisobutyronitrile).
The content of the resin a is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, still more preferably 30 to 70% by mass, and particularly preferably 40 to 60% by mass, based on the total mass of the photosensitive composition layer. From the viewpoint of controlling the development time, the content of the resin a is preferably 90 mass% or less. On the other hand, from the viewpoint of improving the edge melting resistance, the content of the resin a is preferably 10% by mass or more.
The photosensitive composition layer may contain other resins than the resin a described above.
Examples of the other resin include acrylic resins, styrene-acrylic copolymers, polyurethane resins, polyvinyl alcohols, polyvinyl formals, polyester resins, epoxy resins, polyacetal resins, polybenzoxazole resins, polysiloxane resins, polyethyleneimine, polyallylamine and polyalkylene glycols.
(polymerizable Compound)
The photosensitive composition layer may contain a polymerizable compound having a polymerizable group. As the polymerizable compound, an ethylenically unsaturated compound is preferable.
In the present specification, the term "polymerizable compound" refers to a compound different from the resin a and polymerizable by the action of a polymerization initiator described later.
The polymerizable group of the polymerizable compound may be a group participating in polymerization reaction, and examples thereof include groups having an ethylenically unsaturated group such as a vinyl group, an acryloyl group, a methacryloyl group, a styryl group, and a maleimide group; the group having a cationically polymerizable group such as an epoxy group or an oxetanyl group is preferably a group having an ethylenically unsaturated group, and more preferably an acryloyl group or a methacryloyl group.
Examples of the ethylenically unsaturated group of the ethylenically unsaturated compound include a vinyl group, an acryloyl group, a methacryloyl group, a styryl group, and a maleimide group. As the ethylenically unsaturated group, an acryloyl group or a methacryloyl group is preferable.
The polymerizable group of the polymerizable compound other than the ethylenically unsaturated compound is not particularly limited as long as it is a group participating in polymerization reaction, and examples thereof include groups having a cationically polymerizable group such as an epoxy group and an oxetanyl group.
The ethylenically unsaturated compound will be described below.
The ethylenically unsaturated compound is preferably a compound having 2 or more ethylenically unsaturated groups in one molecule (polyfunctional ethylenically unsaturated compound) from the viewpoint of more excellent photosensitivity.
Further, from the viewpoint of more excellent resolution and peelability, the number of ethylenically unsaturated groups contained in one molecule of the ethylenically unsaturated compound is preferably 6 or less, more preferably 3 or less, and further preferably 2 or less.
From the viewpoint of more excellent balance between the photosensitivity, the resolution, and the releasability of the photosensitive composition layer, it is preferable to contain a 2-functional or 3-functional ethylenically unsaturated compound having 2 or 3 ethylenically unsaturated groups in one molecule, and it is more preferable to contain a 2-functional ethylenically unsaturated compound having 2 ethylenically unsaturated groups in one molecule.
From the viewpoint of excellent peelability, the content of the 2-functional ethylenically unsaturated compound with respect to the total mass of the polymerizable compounds is preferably 20% by mass or more, more preferably more than 40% by mass, and further preferably 55% by mass or more. The upper limit is not particularly limited and may be 100 mass%. That is, the polymerizable compounds may be all 2-functional ethylenically unsaturated compounds.
The ethylenically unsaturated compound is preferably a (meth) acrylate compound having a (meth) acryloyl group as a polymerizable group.
Polymerizable compound B1-
The photosensitive composition layer also preferably contains, as a polymerizable compound, a polymerizable compound B1 having an aromatic ring and 2 ethylenically unsaturated groups.
In the photosensitive composition layer, the mass ratio of the content of the polymerizable compound B1 to the total mass of the polymerizable compounds is preferably 40% by mass or more, more preferably 50% by mass or more, further preferably 55% by mass or more, and particularly preferably 60% by mass or more, from the viewpoint of more excellent resolution. The upper limit is not particularly limited, but from the viewpoint of peelability, it is, for example, 100% by mass or less, preferably 99% by mass or less, more preferably 95% by mass or less, further preferably 90% by mass or less, and particularly preferably 85% by mass or less.
Examples of the aromatic ring included in the polymerizable compound B1 include aromatic hydrocarbon rings such as benzene ring, naphthalene ring, and anthracene ring, aromatic heterocyclic rings such as thiophene ring, furan ring, pyrrole ring, imidazole ring, triazole ring, and pyridine ring, and condensed rings thereof, with aromatic hydrocarbon rings being preferred, and benzene rings being more preferred. The aromatic ring may have a substituent.
The polymerizable compound B1 may have only 1 aromatic ring, or may have 2 or more aromatic rings.
The polymerizable compound B1 preferably has a bisphenol structure from the viewpoint of improving the resolution by suppressing swelling of the photosensitive composition layer by the developer.
Examples of the bisphenol structure include a bisphenol a structure derived from bisphenol a (2, 2-bis (4-hydroxyphenyl) propane), a bisphenol F structure derived from bisphenol F (2, 2-bis (4-hydroxyphenyl) methane), and a bisphenol B structure derived from bisphenol B (2, 2-bis (4-hydroxyphenyl) butane), and the bisphenol a structure is preferred.
Examples of the polymerizable compound B1 having a bisphenol structure include compounds having a bisphenol structure and 2 polymerizable groups (preferably (meth) acryloyl groups) bonded to both ends of the bisphenol structure.
The two ends of the bisphenol structure and 2 polymerizable groups can be directly bonded, or can be bonded through 1 or more alkyleneoxy groups, preferably through 1 or more alkyleneoxy groups.
The alkyleneoxy group added to both ends of the bisphenol structure is preferably an ethyleneoxy group or a propyleneoxy group, and more preferably an ethyleneoxy group. The number of addition of alkyleneoxy groups to the bisphenol structure is not particularly limited, but is preferably 4 to 16, more preferably 6 to 14 per 1 molecule.
The polymerizable compound B1 having a bisphenol structure is described in paragraphs [0072] to [0080] of Japanese patent application laid-open No. 2016-224162, the contents of which are incorporated herein by reference.
The polymerizable compound B1 is preferably a 2-functional ethylenically unsaturated compound having a bisphenol a structure, and more preferably 2, 2-bis (4- ((meth) acryloyloxyalkyloxy) phenyl) propane.
Examples of the 2, 2-bis (4- ((meth) acryloyloxyalkyl polyalkoxy) phenyl) propane include 2, 2-bis (4- (methacryloyloxydiethoxy) phenyl) propane (FA-324M, manufactured by Hitachi Chemical Co., ltd.), 2-bis (4- (methacryloyloxyethoxypropoxy) phenyl) propane, 2-bis (4- (methacryloyloxypentaethoxy) phenyl) propane (BPE-500, manufactured by Shin-Nakamura Chemical Co., ltd.), 2-bis (4- (methacryloyloxydodecaethoxytetrapropoxy) phenyl) propane (FA-MY, hitachi Chemical Co., manufactured by Shitd Chemical), 2-bis (4- (methacryloyloxypentadecyloxy) phenyl) propane (BPE-1300, 2-bis (4- (methacryloyloxydiethoxy) phenyl) propane (BPE-1300, 2-Nakamura Co., manufactured by Shitdo Chemical Co., ltd.), 2-bis (4- (methacryloyloxydiethoxy) phenyl) propane (BPE-200, manufactured by Shitde Chemical Co., ltd.), bisphenol A-10, manufactured by Shitdkamura Chemical Co., ltd.), and bisphenol A-10, manufactured by Shitachi Chemical Co., ltd.).
The polymerizable compound B1 may be used alone or in combination of two or more.
From the viewpoint of more excellent resolution, the content of the polymerizable compound B1 is preferably 10 mass% or more, and more preferably 20 mass% or more, with respect to the total mass of the photosensitive composition layer. The upper limit is not particularly limited, but is preferably 70% by mass or less, more preferably 60% by mass or less, from the viewpoint of transferability and edge melting (a phenomenon in which the photosensitive resin bleeds out from the end of the transfer member).
The polymerizable compound is preferably a polymerizable compound having an alkylene oxide-modified bisphenol structure, and more preferably a compound represented by the following general formula (B1) (also corresponding to the polymerizable compound B1).
[ chemical formula 4]
In the general formula (B1), R 1 And R 2 Each independently represents a hydrogen atom or a methyl group. A represents C 2 H 4 . B represents C 3 H 6 . n1 and n3 are each independently an integer of 1 to 39, and n1+ n3 is an integer of 2 to 40. n2 and n4 are each independently an integer of 0 to 29, and n2+ n4 is an integer of 0 to 30. The arrangement of the structural units- (A-O) -and- (B-O) -may be random, it may be a block. Also, in the case of a block, either one of- (A-O) -and- (B-O) -may be on the biphenyl (bisphenyl) side.
In one aspect, n1+ n2+ n3+ n4 is preferably 2 to 20, more preferably 2 to 16, and further preferably 4 to 12. N2+ n4 is preferably 0 to 10, more preferably 0 to 4, further preferably 0 to 2, particularly preferably 0.
The photosensitive composition layer may contain other polymerizable compounds than the polymerizable compounds described above.
The other polymerizable compound is not particularly limited, and can be appropriately selected from known compounds. Examples thereof include a compound having 1 ethylenically unsaturated group in one molecule (monofunctional ethylenically unsaturated compound), a 2-functional ethylenically unsaturated compound having no aromatic ring, and an ethylenically unsaturated compound having 3 or more functions.
Examples of the monofunctional ethylenically unsaturated compound include ethyl (meth) acrylate, ethylhexyl (meth) acrylate, 2- (meth) acryloyloxyethyl succinate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, and phenoxyethyl (meth) acrylate.
Examples of the 2-functional ethylenically unsaturated compound having no aromatic ring include alkylene glycol di (meth) acrylate, polyalkylene glycol di (meth) acrylate, urethane di (meth) acrylate, and trimethylolpropane diacrylate.
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Examples of the polyalkylene glycol di (meth) acrylate include polyethylene glycol di (meth) acrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate and polypropylene glycol di (meth) acrylate.
Examples of the urethane di (meth) acrylate include propylene oxide-modified urethane di (meth) acrylate and ethylene oxide-and propylene oxide-modified urethane di (meth) acrylate. Examples of commercially available products include 8UX-015A (manufactured by Taisei Fine Chemical Co., ltd.), UA-32P (manufactured by Shin-Nakamura Chemical Co., ltd.), and UA-1100H (manufactured by Shin-Nakamura Chemical Co., ltd.).
Examples of the ethylenically unsaturated compound having 3 or more functions include dipentaerythritol (tri/tetra/penta/hexa) (meth) acrylate, pentaerythritol (tri/tetra) (meth) acrylate, trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, trimethylolethane tri (meth) acrylate, isocyanuric acid tri (meth) acrylate, glycerol tri (meth) acrylate, and alkylene oxide modified products thereof.
In the above description, "(tri/tetra/penta/hexa) (meth) acrylate" is a concept including tri (meth) acrylate, tetra (meth) acrylate, penta (meth) acrylate and hexa (meth) acrylate, and "(tri/tetra) (meth) acrylate" is a concept including tri (meth) acrylate and tetra (meth) acrylate.
In one aspect, the photosensitive composition layer preferably contains the polymerizable compound B1 and an ethylenically unsaturated compound having 3 or more functions, and more preferably contains the polymerizable compound B1 and two or more ethylenically unsaturated compounds having 3 or more functions. In this case, the mass ratio of the polymerizable compound B1 to the 3-or more-functional ethylenically unsaturated compound is preferably (the total mass of the polymerizable compounds B1 to (the total mass of the 3-or more-functional ethylenically unsaturated compounds) = 1:1 to 5:1, more preferably 1.2: 1 to 4: 1, and still more preferably 1.5: 1 to 3: 1.
In one embodiment, the photosensitive composition layer preferably contains the polymerizable compound B1 and two or more 3-functional ethylenically unsaturated compounds.
Examples of the alkylene oxide-modified product of the ethylenically unsaturated compound having 3 or more functional groups include caprolactone-modified (meth) acrylate compounds (kaparad (registered trademark) DPCA-20, shin-Nakamura Chemical co., manufactured by Nippon Kayaku co., ltd., a-9300-1CL manufactured by ltd., etc.), ethoxylated trimethylolpropane trimethacrylate (TOMOE Engineering co., SR454, SR499, SR502, etc. manufactured by ltd., etc.), alkylene oxide-modified (meth) acrylate compound (Nippon Kayaku co., ltd., KAYARAD RP-1040 manufactured by Ltd., shin-Nakamura Chemical Co., ATM-35E manufactured by Ltd., A-9300 manufactured by Ltd., EBECRYL (registered trademark) 135 manufactured by DAICEL-ALLNEX LTD., etc.), ethoxylated glycerol trimethacrylate (Shin-Nakamura Chemical Co., ltd., ltd. Manufactured a-GLY-9E, etc.), ARONIX (registered trademark) T0-2349 (TOAGOSEI co., ltd., manufactured), ARONIX M-520 (TOAGOSEI co., ltd., manufactured), and ARONIX M-510 (TOA GOSEI co., ltd., manufactured).
As the polymerizable compound, a polymerizable compound having an acid group (e.g., a carboxyl group) can be used. The acid groups may form anhydride groups. Examples of the polymerizable compound having an acid group include ARONIX (registered trademark) TO-2349 (manufactured by TOAGOSEI co., ltd.), ARONIX (registered trademark) M-520 (manufactured by TOAGOSEI co., ltd.), and ARONIX (registered trademark) M-510 (manufactured by TOAGOSEI co., ltd.).
Examples of the polymerizable compound having an acid group include polymerizable compounds having an acid group described in paragraphs [0025] to [0030] of Japanese patent application laid-open No. 2004-239942.
The molecular weight (weight average molecular weight when having a molecular weight distribution) of the polymerizable compound (including the polymerizable compound B1) is preferably 200 to 3000, more preferably 280 to 2200, and still more preferably 300 to 2200.
One or more polymerizable compounds may be used alone or in combination.
The content of the polymerizable compound is preferably 0 to 70% by mass, more preferably 10 to 70% by mass, and still more preferably 20 to 60% by mass, based on the total mass of the photosensitive composition layer.
(polymerization initiator)
The photosensitive composition layer may contain a polymerization initiator.
As the polymerization initiator, for example, a known polymerization initiator can be used depending on the form of the polymerization reaction. Specifically, a thermal polymerization initiator and a photopolymerization initiator can be mentioned.
The polymerization initiator may be any of radical polymerization initiators and cationic polymerization initiators.
The photosensitive composition layer preferably contains a photopolymerization initiator.
The photopolymerization initiator is a compound that initiates polymerization of the polymerizable compound upon receiving actinic rays such as ultraviolet rays, visible rays, and X-rays. The photopolymerization initiator is not particularly limited, and a known photopolymerization initiator can be used.
Examples of the photopolymerization initiator include a photo radical polymerization initiator and a photo cation polymerization initiator, and a photo radical polymerization initiator is preferable.
Examples of the photo radical polymerization initiator include a photopolymerization initiator having an oxime ester structure, a photopolymerization initiator having an α -aminoalkylphenone structure, a photopolymerization initiator having an α -hydroxyalkylphenone structure, a photopolymerization initiator having an acylphosphine oxide structure, and a photopolymerization initiator having an N-phenylglycine structure.
In addition, from the viewpoint of photosensitivity, visibility and resolution of an exposed portion and a non-exposed portion, the photosensitive composition layer preferably contains at least one selected from 2,4, 5-triarylimidazole dimer and its derivative as a photoradical polymerization initiator. In addition, 2,4, 5-triarylimidazole dimers and derivatives thereof may have the same or different 2,4, 5-triarylimidazole structures.
Examples of the derivatives of the 2,4, 5-triarylimidazole dimer include 2- (o-chlorophenyl) -4, 5-diphenylimidazole dimer, 2- (o-chlorophenyl) -4, 5-bis (methoxyphenyl) imidazole dimer, 2- (o-fluorophenyl) -4, 5-diphenylimidazole dimer, 2- (o-methoxyphenyl) -4, 5-diphenylimidazole dimer, and 2- (p-methoxyphenyl) -4, 5-diphenylimidazole dimer.
As the photo radical polymerization initiator, for example, the polymerization initiators described in paragraphs [0031] to [0042] of Japanese patent application laid-open No. 2011-095716 and paragraphs [0064] to [0081] of Japanese patent application laid-open No. 2015-014783 can be used.
Examples of the photo-radical polymerization initiator include ethyl dimethylaminobenzoate (DBE, CAS No. 10287-53-3), benzoin methyl ether, (p, p '-dimethoxybenzyl) anise ester, TAZ-110 (trade name: midori Kagaku Co., ltd.), benzophenone, 4' -bis (diethylamino) benzophenone, TAZ-111 (trade name: midori Kagaku Co., ltd.), irgacUre 01, OXE02, OXE03, OXE04 (BASF Co., ltd.), omnirad651 and 369 (trade name: IGM ins B.V., ltd.), and 2,2 '-bis (2-chlorophenyl) -4,4',5 '-tetraphenyl-1, 2' -biimidazole (Tokyo Industry Co., ltd.).
Examples of commercially available products of the photoradical polymerization initiator include 1- [4- (phenylthio) phenyl ] -1, 2-octanedione-2- (O-benzoyl oxime) (trade name: IRGACURE (registered trademark) OXE-01, manufactured by BASF corporation), 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] ethanone-1- (O-acetyloxime) (trade name: IRGACURE OXE-02, manufactured by BASF corporation), IRGACURE OXE-03 (manufactured by BASF corporation), IRGACURE OXE-04 (manufactured by BASF corporation), 2- (dimethylamino) -2- [ (4-methylphenyl) methyl ] -1- [4- (4-morpholino) phenyl ] -1-butanone (trade name: omnirad) methyl ethyl ketone (trade name: EG 9, manufactured by IGM Resins B.V.), 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one (trade name: omniins Res. V), 2-methyl-1- (4-morpholinopropan-1-one (trade name: omniins Res. V), 2-hydroxy-benzyl-2- (2-morpholino-propionyl) -1- (2-morpholino-methyl-2-propanone (trade name: omnirs B.V): omnirad 369, igm Resins b.v.), 2-hydroxy-2-methyl-1-phenylpropan-1-one (trade name: omnirad 1173, igm Resins b.v.), 1-hydroxycyclohexyl phenyl ketone (trade name: omnirad 184, manufactured by igm Resins b.v.), 2-dimethoxy-1, 2-diphenylethan-1-one (trade name: omnirad651, igm Resins b.v., manufactured), 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide (trade name: omnirad TPO H, manufactured by IGM Resins b.v.), bis (2, 4, 6-trimethylbenzoyl) phenylphosphine oxide (trade name: omnirad 819, manufactured by igm Resins b.v.), a photopolymerization initiator of oxime ester type (trade name: lunar 6, dksh Japan k.k.), 2' -bis (2-chlorophenyl) -4,4', 5' -tetraphenylbiimidazole (2- (2-chlorophenyl) -4, 5-diphenylimidazole dimer) (trade name: B-CIM manufactured by Hampford corporation), 2- (o-chlorophenyl) -4, 5-diphenylimidazole dimer (trade name: BCTB, tokyo Chemical Industry co., ltd., manufactured), 1- [4- (phenylthio) phenyl ] -3-cyclopentylpropane-1, 2-dione-2- (O-benzoyl oxime) (trade name: TR-PBG-305, changzhou Tronly New Electronic Materials CO, ltd., manufactured), 1, 2-propanedione, 3-cyclohexyl-1- [ 9-ethyl-6- (2-furylcarbonyl) -9H-carbazol-3-yl 1-,2- (O-acetyloxime) (trade name: TR-PBG-326, changzhou Tronly New Electronic Materials CO, ltd.) and 3-cyclohexyl-1- (6- (2- (benzoyloxyimino) octanoyl) -9-ethyl-9H-carbazol-3-yl) -propane-1, 2-dione-2- (0-benzoyloxime) (trade name: TR-PBG-391, changzhou Tronly New Electronic Materials CO., LTD.
The photo cation polymerization initiator (photo acid generator) is a compound that receives actinic rays to generate an acid. The photo cation polymerization initiator is preferably a compound which generates an acid by being responsive to actinic rays having a wavelength of 300nm or more, preferably 300nm to 450nm, but the chemical structure is not limited. The photo cation polymerization initiator that is not directly sensitive to actinic rays having a wavelength of 300nm or more may be preferably used in combination with a sensitizer as long as it is a compound that generates an acid by being sensitive to actinic rays having a wavelength of 300nm or more when used in combination with the sensitizer.
As the photo cation polymerization initiator, a photo cation polymerization initiator that generates an acid having a pKa of 4 or less is preferable, a photo cation polymerization initiator that generates an acid having a pKa of 3 or less is more preferable, and a photo cation polymerization initiator that generates an acid having a pKa of 2 or less is even more preferable. The lower limit of the pKa is not particularly limited, but is preferably at least-10.0.
Examples of the photo cation polymerization initiator include ionic photo cation polymerization initiators and nonionic photo cation polymerization initiators.
Examples of the ionic photo-cationic polymerization initiator include onium salt compounds such as diaryliodonium salts and triarylsulfonium salts, and quaternary ammonium salts.
As the ionic photo cation polymerization initiator, the ionic photo cation polymerization initiators described in paragraphs [0114] to [0133] of Japanese patent application laid-open Nos. 2014-085643 can be used.
Examples of the nonionic photo cation polymerization initiator include trichloromethyl-s-triazines, diazomethane compounds, imide sulfonate compounds and oxime sulfonate compounds. As the trichloromethyl-s-triazine, diazomethane compound and imide sulfonate compound, compounds described in paragraphs [0083] to [0088] of jp 2011-221494 a can be used. Furthermore, as the oxime sulfonate compound, compounds described in paragraphs [0084] to [0088] of International publication No. 2018/179640 can be used.
The photosensitive composition layer preferably contains a photo radical polymerization initiator, and more preferably contains at least one selected from the group consisting of 2,4, 5-triarylimidazole dimers and derivatives thereof.
One kind of the polymerization initiator may be used alone, or two or more kinds may be used.
The content of the polymerization initiator (preferably, photopolymerization initiator) is not particularly limited, but is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and further preferably 1.0% by mass or more, relative to the total mass of the photosensitive composition layer. The upper limit is not particularly limited, but is preferably 20% by mass or less, more preferably 15% by mass or less, and further preferably 10% by mass or less, relative to the total mass of the photosensitive composition layer.
(sensitizer)
The photosensitive composition layer preferably contains a sensitizer.
The sensitizer is not particularly limited, and a known sensitizer, dye, and pigment can be used. Examples of the sensitizer include dialkylaminobenzophenone compounds, pyrazoline compounds, anthracene compounds, coumarin compounds, xanthenone (xanthone) compounds, thioxanthone (thioxanthone) compounds, acridone compounds, oxazole compounds, benzoxazole compounds, thiazole compounds, benzothiazole compounds, triazole compounds (e.g., 1,2, 4-triazole), stilbene compounds, distyrylbenzene (distyrylbenzene), styrylbenzene (styrylbenzene), triazine compounds, thiophene compounds, naphthalimide compounds, triarylamine compounds, and aminoacridine compounds. In addition, the above-listed compounds also include derivatives of the above-mentioned compounds.
Among them, as the sensitizer, a dialkylaminobenzophenone compound, an anthracene compound, a distyrylbenzene compound, or a styrylpyridine compound is preferable, an anthracene compound, a distyrylbenzene compound, or a styrylpyridine compound is more preferable, and an anthracene derivative, a distyrylbenzene derivative, or a styrylpyridine derivative is further preferable.
One or more kinds of the sensitizer may be used alone.
When the photosensitive composition layer contains a sensitizer, the content of the sensitizer can be appropriately selected according to the purpose, but from the viewpoint of improving the sensitivity to a light source and improving the curing rate by the balance of the polymerization rate and the chain transfer, it is preferably 0.01 to 5% by mass, more preferably 0.05 to 1% by mass, relative to the total mass of the photosensitive composition layer.
(pigments)
From the viewpoint of visibility of exposed portions and non-exposed portions, pattern visibility after development, and resolution, the photosensitive composition layer preferably contains a dye (also referred to as "dye N") having a maximum absorption wavelength of 450nm or more in a wavelength range of 400 to 780nm during color development and a maximum absorption wavelength that changes by an acid, an alkali, or a radical. When the pigment N is contained, although the detailed mechanism is not clear, the adhesion with an adjacent layer (for example, a water-soluble resin layer) is improved and the resolution is further excellent.
In the present specification, the "change in the maximum absorption wavelength of a dye by an acid, an alkali, or a radical" may refer to any one of a method in which a dye in a developed state is decolorized by an acid, an alkali, or a radical, a method in which a dye in a decolorized state is developed by an acid, an alkali, or a radical, and a method in which a dye in a developed state is changed to a developed state of another color.
Specifically, the dye N may be a compound that develops color by changing from a decolored state by exposure, or may be a compound that develops color by changing from a colored state by exposure. In this case, the dye may be one in which an acid, a base, or a radical is generated in the photosensitive composition layer by exposure and acts to change the color development or the color removal state, or one in which the state (for example, pH) in the photosensitive composition layer is changed by an acid, a base, or a radical to change the color development or the color removal state. Further, the dye may be one which changes its color development or decoloration state by being directly stimulated by an acid, an alkali, or a radical without exposure.
Among them, the dye N is preferably a dye whose maximum absorption wavelength is changed by an acid or a radical, and more preferably a dye whose maximum absorption wavelength is changed by a radical, from the viewpoint of visibility and resolution of an exposed portion and a non-exposed portion.
When the photosensitive composition layer is a negative photosensitive composition layer, the negative photosensitive composition layer preferably contains a pigment whose maximum absorption wavelength is changed by a radical as both the pigment N and the photo radical polymerization initiator, from the viewpoint of visibility and resolution of an exposed portion and a non-exposed portion.
The dye N is preferably a dye that develops color by an acid, an alkali, or a radical, from the viewpoint of visibility of the exposed portion and the unexposed portion.
Examples of the color developing mechanism of the dye N include a method in which a radical reactive dye, an acid reactive dye, or a base reactive dye (for example, leuco dye) is developed by adding a photo radical polymerization initiator, a photo cation polymerization initiator (photo acid generator), or a photo base generator to a photosensitive composition layer, followed by exposure, and then by a radical, an acid, or a base generated by the photo radical polymerization initiator, the photo cation polymerization initiator, or the photo base generator.
From the viewpoint of visibility of the exposed portion and the non-exposed portion, the maximum absorption wavelength in the wavelength range of 400 to 780nm in color development of the dye N is preferably 550nm or more, more preferably 550 to 700nm, and still more preferably 550 to 650nm.
The dye N may have only the maximum absorption wavelength in the wavelength range of 400 to 780nm in the case of 1 color development, or may have 2 or more. When the dye N has 2 or more maximum absorption wavelengths in the wavelength range of 400 to 780nm at the time of color development, the maximum absorption wavelength having the highest absorbance among the 2 or more maximum absorption wavelengths may be 450nm or more.
The maximum absorption wavelength of the pigment N is determined by using a spectrophotometer under an atmospheric environment: UV3100 (manufactured by Shimadzu Corporation) is obtained by measuring the transmission spectrum of a solution containing a dye N (liquid temperature 25 ℃) in the wavelength range of 400nm to 780nm and detecting the wavelength (maximum absorption wavelength) at which the intensity of light is extremely small.
Examples of the dye that develops color or decolors by exposure include colorless compounds.
Examples of the coloring matter decolorized by exposure to light include a leuco compound, diarylmethane-based coloring matter, oxazine-based coloring matter, xanthene-based coloring matter, iminonaphthoquinone-based coloring matter, azomethine-based coloring matter, and anthraquinone-based coloring matter.
The dye N is preferably a colorless compound from the viewpoint of visibility of an exposed portion and a non-exposed portion.
Examples of the colorless compound include a colorless compound having a triarylmethane skeleton (triarylmethane-based dye), a colorless compound having a spiropyran skeleton (spiropyran-based dye), a colorless compound having a fluoran skeleton (fluoran-based dye), a colorless compound having a diarylmethane skeleton (diarylmethane-based dye), a colorless compound having a rhodamine lactam skeleton (rhodamine lactam-based dye), a colorless compound having an indolylphthalein skeleton (indolylphthalein-based dye), and a colorless compound having a leuco auramine skeleton (leuco auramine-based dye).
Among them, triarylmethane-based dyes or fluoran-based dyes are preferable, and leuco compounds having a triphenylmethane skeleton (triphenylmethane-based dyes) or fluoran-based dyes are more preferable.
The colorless compound preferably has a lactone ring, a sulfinyl lactone ring (sultone ring), or a sultone ring from the viewpoint of visibility of an exposed portion and a non-exposed portion. Thus, the lactone ring, sulfinolactone ring or sultone ring of the colorless compound can be reacted with the radical generated by the photo radical polymerization initiator or the acid generated by the photo cation polymerization initiator to change the colorless compound into a closed ring state and decolorize the colorless compound, or the colorless compound can be changed into an open ring state and develop the color. As the colorless compound, a compound having a lactone ring, sulfinyl lactone ring, or sultone ring, which develops color by radical or acid ring opening, is preferable, and a compound having a lactone ring, which develops color by radical or acid ring opening, is more preferable.
Examples of the dye N include the following dyes and leuco compounds.
Specific examples of the dye N include brilliant green (brilliant green), ethyl violet, methyl green, crystal violet, basic fuchsin (basic fuchsin), methyl violet 2B, quinaldine red (quinaldine red), rose bengal (rose bengal), metanil yellow (metanil yellow), thymol sulfonphthalein (thymol sulfonphthalein), xylenol (xylenol) blue, methyl orange, p-methyl red, congo red, benzo-erythrosine (benzopurpurine) 4B, a-naphthyl red, nile blue (blue) 2B, nile blue a, methyl violet, malachite green (malachite green), paraffinin (paraffinin), victoria pure blue (vitamin blue) -naphthalene sulfonate, victoria pure blue h (bodoya green), oil blue # co (Chemical co 603, chemical co, 603, and so on), and so on ltd., manufactured), oil pink red #312 (Orien Chemical Industries co., ltd., manufactured), oil red 5B (Orien Chemical Industries co., ltd., manufactured), oil scarlet (oil scarlet) #308 (Orien Chemical Industries co., ltd., manufactured), oil red 0G (Orien Chemical Industries co., ltd., manufactured), oil red RR (Orien Chemical Industries co., ltd., manufactured), oil green #502 (Orien Chemical Industries co., ltd., manufactured), steilon red (spilon red) BEH (Hodogaya Chemical co., ltd., manufactured), cresol red, rhodamine B, rhodamine 6G, sulforhodamine B, auramine, 4-p-diethylaminophenyliminoquinone, 2-carboxy-p-aminophenylquinonyl-4-diethylaminophenyliminoquinone, 2-carboxystearylamino-4-p-N, N-bis (hydroxyethyl) amino-phenylimino-naphthoquinone, 1-phenyl-3-methyl-4-p-diethylaminophenylimino-5-pyrazolone and 1- β -naphthyl-4-p-diethylaminophenylimino-5-pyrazolone.
<xnotran> N , , p, p', p "- ( ), pergascript Blue SRB (Ciba-Geigy ), , , ,2- (N- -N- ) -6- (N- -N- ) ,2- -3- -6- (N- - ) ,3,6- ,3- (N, N- ) -5- -7- (N, N- ) ,3- (N- -N- ) -6- -7- ,3- (N, N- ) -6- -7- ,3- (N, N- ) -6- -7- ,3- (N, N- ) -6- -7- ,3- (N, N- ) -6- -7- ,3- (N, N- ) -7- (4- ) , </xnotran> 3- (N, N-diethylamino) -7-chlorofluorane, 3- (N, N-diethylamino) -7-benzylaminofluorane, 3- (N, N-diethylamino) -7, 8-benzofluorane, 3- (N, N-dibutylamino) -6-methyl-7-anilinofluorane, 3-piperidinyl-6-methyl-7-anilinofluorane, 3-pyrrolidinyl-6-methyl-7-anilinofluorane, 3-bis (1-ethyl-2-methylindol-3-yl) phthalein lactone (phthalide), 3-bis (1-N-butyl-2-methylindol-3-yl) phthalein lactone, 3-bis (p-dimethylaminophenyl) -6-dimethylaminophthalein lactone, 3- (4-diethylamino-2-ethoxyphenyl) -3- (1-ethyl-2-methylindol-3-yl) -4-azaindolespironolactone, 3' -diethyl-2-ethoxyphenyl) -3- (1-ethyl-2-methylindol-3-yl) -4-azaindolespironolactone, and 3' -bis (1-ethyl-2-methylindol-3 ' -diphenylaminophthalein lactone), 9' - [9H ] xanthen-3-one.
The dye N is preferably a dye whose maximum absorption wavelength changes by a radical, and more preferably a dye whose color develops by a radical, from the viewpoints of the visibility of exposed portions and unexposed portions, the pattern visibility after development, and the resolution.
As the pigment N, leuco crystal violet, crystal violet lactone, brilliant green, or victoria pure blue-naphthalene sulfonate is preferable.
One kind of the pigment N may be used alone, or two or more kinds thereof may be used.
The content of the dye N is preferably 0.1% by mass or more, more preferably 0.1 to 10% by mass, even more preferably 0.1 to 5% by mass, and particularly preferably 0.1 to 1% by mass, based on the total mass of the photosensitive composition layer, from the viewpoints of visibility of exposed portions and non-exposed portions, pattern visibility after development, and resolution.
The content of the pigment N is a content of the pigment when all the pigments N contained in the total mass of the photosensitive composition layer are in a colored state. Hereinafter, a method for quantifying the content of pigment N will be described by taking a pigment that develops color by a radical as an example.
A solution was prepared by dissolving 0.001g and 0.01g of a dye in 100mL of methyl ethyl ketone. To each of the obtained solutions, a photo radical polymerization initiator (trade name, irgacure OXE01, manufactured by BASF japan ltd.) was added, and light having a wavelength of 365nm was irradiated, thereby generating radicals to bring all the dyes into a colored state. Then, the absorbance of each solution at a liquid temperature of 25 ℃ was measured using a spectrophotometer (UV 3100, manufactured by Shimadzu Corporation) under an atmospheric environment, and a calibration curve was prepared.
Next, the absorbance of the solution in which all the pigments were developed was measured by the same method as described above except that 3g of the photosensitive composition layer was dissolved in methyl ethyl ketone instead of the pigments. The content of the pigment contained in the photosensitive composition layer was calculated from the absorbance of the obtained solution containing the photosensitive composition layer based on the calibration curve.
The photosensitive composition layer 3g was the same as the photosensitive composition layer 3g in terms of total solid content.
(pigments)
The photosensitive composition layer may contain a pigment.
When the photosensitive composition layer contains a pigment, the photosensitive composition layer corresponds to the colored resin layer.
In recent years, a cover glass (cover glass) having a black frame-shaped light shielding layer formed on a peripheral edge portion of a back surface of a transparent glass substrate or the like is sometimes attached to a liquid crystal display window included in an electronic device in order to protect the liquid crystal display window. In order to form such a light-shielding layer, a colored resin layer may be used.
The pigment may be appropriately selected depending on the desired hue, and examples thereof include a black pigment, a white pigment, and a color pigment other than black and white, and in the case of forming a black pattern, a black pigment is preferable.
Examples of the black pigment include known black pigments (for example, organic pigments and inorganic pigments).
Among them, from the viewpoint of optical density, carbon black, titanium oxide, titanium carbide, iron oxide, or graphite is preferable as the black pigment, and carbon black is more preferable. As the carbon black, a surface-modified carbon black in which at least a part of the surface is coated with a resin is preferable from the viewpoint of surface resistance.
From the viewpoint of dispersion stability, the particle diameter (number average particle diameter) of the black pigment is preferably 0.001 to 0.1. Mu.m, more preferably 0.01 to 0.08. Mu.m.
The "particle diameter" refers to the diameter of a circle when the area of the pigment particle is determined from a photographic image of the pigment particle taken with an electron microscope and the circle having the same area as the area of the pigment particle is considered. The "number average particle size" refers to an average value obtained by obtaining the particle size for any 100 particles and averaging the obtained 100 particle sizes.
Examples of the white pigment include inorganic pigments and white pigments described in paragraphs [0015] and [0114] of Japanese patent application laid-open No. 2005-007765.
As the inorganic pigment, titanium oxide, zinc oxide, lithopone, light calcium carbonate, white carbon, aluminum oxide, aluminum hydroxide, or barium sulfate is preferable, titanium oxide or zinc oxide is more preferable, titanium oxide is further preferable, rutile-type or anatase-type titanium oxide is particularly preferable, and rutile-type titanium oxide is most preferable.
The surface of the titanium oxide may be subjected to silica treatment, alumina treatment, titania treatment, zirconia treatment, or organic matter treatment, or two or more of these treatments may be performed. This suppresses the catalytic activity of titanium oxide, and improves the heat resistance and the light fading property.
From the viewpoint of reducing the thickness of the photosensitive composition layer after heating, at least one of the alumina treatment and the zirconia treatment is preferably performed as the surface treatment of the surface of the titanium oxide, and more preferably both of the alumina treatment and the zirconia treatment are performed.
When the photosensitive composition layer is a colored resin layer, the photosensitive composition layer preferably contains a color pigment other than a black pigment and a white pigment from the viewpoint of transferability.
The particle diameter (number average particle diameter) of the color pigment is preferably 0.1 μm or less, more preferably 0.08 μm or less, from the viewpoint of more excellent dispersibility. The lower limit is preferably 10nm or more.
Examples of the Color pigment include victoria pure blue BO (Color Index) (hereinafter, also referred to as "c.i.") 42595), auramine (c.i.41000), fat black (fat black) HB (c.i.26150), morronite yellow (monolithic yellow) GT (c.i. pigment yellow 12), permanent yellow (permanent yellow) GR (c.i. pigment yellow 17), permanent yellow HR (c.i. pigment yellow 83), permanent carmine (permanent carmine) FBB (c.i. pigment red 146), huskbam red (hostaperm red) ESB (c.i. pigment violet 19), permanent ruby red (permanentruby) FBH (c.i. pigment red 11), french red (pura) B (pura) (c.i. pigment red 149), black pigment red (c.i. pigment red) 122, c.i. pigment red 168, c.i. pigment red 177, c.i. pigment red 15, c.i. pigment red (c.i. pigment red) white pigment red 168, c.i. pigment red 177, c.i. pigment red 168, c.e. pigment red: 1. c.i. pigment blue 15: 4. c.i. pigment blue 22, c.i. pigment blue 60, c.i. pigment blue 64 and c.i. pigment violet 23, preferably c.i. pigment red 177.
One pigment may be used alone, or two or more pigments may be used.
The content of the pigment is preferably more than 3% by mass and 40% by mass or less, more preferably more than 3% by mass and 35% by mass or less, further preferably more than 5% by mass and 35% by mass or less, and particularly preferably 10 to 35% by mass, based on the total mass of the photosensitive composition layer.
When the photosensitive composition layer contains a pigment other than a black pigment (for example, a white pigment, a color pigment, or the like), the content of the pigment other than the black pigment is preferably 30% by mass or less, more preferably 1 to 20% by mass, and further preferably 3 to 15% by mass, relative to the total mass of the black pigment.
When the photosensitive composition layer contains a black pigment, the black pigment (preferably, carbon black) is preferably introduced into the photosensitive composition in the form of a pigment dispersion.
The dispersion liquid may be prepared by adding a mixture obtained by mixing the black pigment and the pigment dispersant in advance to an organic solvent (or vehicle) and dispersing with a dispersing machine. The pigment dispersant may be selected according to the pigment and the solvent, and for example, a commercially available dispersant can be used.
The "vehicle" refers to a medium portion for dispersing the pigment when the pigment dispersion is prepared. The vehicle is in a liquid state and includes a binder component for holding the black pigment in a dispersed state and a solvent component (organic solvent) for dissolving and diluting the binder component.
Examples of the dispersing machine include known dispersing machines such as a kneader, a roll mill, an attritor, a super mill, a dissolver, a homomixer, and a sand mill.
Further, the fine grinding may be performed by mechanical grinding and utilizing a frictional force. Examples of the dispersing machine and the fine pulverization include a "pigment dictionary" (written by shanghao, first edition, shoji bookshop, 2000, 438, and 310 pages).
(other additives)
The photosensitive composition layer may contain known additives as needed, in addition to the above components.
Examples of the additives include radical polymerization inhibitors, antioxidants (e.g., phenidone), rust inhibitors (e.g., benzotriazoles and carboxybenzotriazoles), sensitizers, surfactants, plasticizers, heterocyclic compounds (e.g., triazole), pyridines (e.g., isonicotinamide), and purine bases (e.g., adenine).
Examples of the other additives include metal oxide particles, a chain transfer agent, an antioxidant, a dispersant, an acid-proliferating agent, a development accelerator, conductive fibers, an ultraviolet absorber, a thickener, a crosslinking agent, an organic or inorganic precipitation inhibitor, and paragraphs [0165] to [0184] of jp 2014-085643 a, which are incorporated herein.
Each additive may be used alone or in combination of two or more.
The photosensitive composition layer may contain a radical polymerization inhibitor.
Examples of the radical polymerization inhibitor include thermal polymerization inhibitors described in paragraph [0018] of Japanese patent No. 4502784. Among them, phenothiazine, phenoxazine or 4-methoxyphenol is preferable. Examples of the other radical polymerization inhibitors include naphthylamine, cuprous chloride, N-nitrosophenylhydroxylamine aluminum salt, and diphenylnitrosamine. In order not to impair the sensitivity of the photosensitive composition layer, an N-nitrosophenylhydroxylamine aluminum salt is preferably used as a radical polymerization inhibitor.
The content of the radical polymerization inhibitor is preferably 0.005 to 5.0% by mass, more preferably 0.01 to 3.0% by mass, and still more preferably 0.01 to 1.0% by mass, based on the total mass of the polymerizable compounds.
Examples of the benzotriazole include 1,2, 3-benzotriazole, 1-chloro-1, 2, 3-benzotriazole, bis (N-2-ethylhexyl) aminomethylene-1, 2, 3-tolyltriazole, and bis (N-2-hydroxyethyl) aminomethylene-1, 2, 3-benzotriazole.
Examples of the carboxybenzotriazole include 4-carboxy-1, 2, 3-benzotriazole, 5-carboxy-1, 2, 3-benzotriazole, N- (N, N-di-2-ethylhexyl) aminomethylene carboxybenzotriazole, N- (N, N-di-2-hydroxyethyl) aminomethylene carboxybenzotriazole, and N- (N, N-di-2-ethylhexyl) aminoethylene carboxybenzotriazole. As the carboxybenzotriazole, for example, a commercially available product such as CBT-1 (johakuchemicalco, ltd., trade name) can be used.
The total content of the benzotriazole and carboxybenzotriazole is preferably 0.01 to 3% by mass, more preferably 0.05 to 1% by mass, based on the total mass of the photosensitive composition layer. When the content is 0.01% by mass or more, the storage stability of the photosensitive composition layer is more excellent. On the other hand, when the content is 3% by mass or less, the maintenance of sensitivity and the inhibition of discoloration of the dye are more excellent.
Examples of the surfactant include surfactants described in paragraph [0017] of Japanese patent publication No. 4502784 and paragraphs [0060] to [0071] of Japanese patent application laid-open No. 2009-237362.
The surfactant is preferably a nonionic surfactant, a fluorine surfactant, or a silicone surfactant.
<xnotran> , MEGAFACE F-171, F-172, F-173, F-176, F-177, F-141, F-142, F-143, F-144, F-437, F-475, F-477, F-479, F-482, F-551-A, F-552, F-554, F-555-A, F-556, F-557, F-558, F-559, F-560, F-561, F-565, F-563, F-568, F-575, F-780, EXP.MFS-330, EXP.MFS-578, EXP.MFS-579, EXP.MFS-586, EXP.MFS-587, EXP.MFS- -628, EXP.MFS-631, EXP.MFS-603, R-41, R-41-LM, R-01, R-40, R-40-LM, RS-43, TF-1956, RS-90, R-94, RS-72-K, DS-21 ( DIC Corporation ), fluorad FC430, FC431, FC171 ( Sumitomo 3M Limited ), surflon S-382, SC-101, SC-103, SC-104, SC-105, SC-1068, SC-381, SC-383, S-393, KH-40 ( AGC Inc. ), polyFox PF636, PF656, PF6320, PF6520, PF7002 ( OMNOVA Solutions Inc. ), ftergent 710FL, 710FM, 610FM, 601AD, 601ADH2, 602A, 215M, 245F, 251, 212M, 250, 209F, 222F, 208G, 710LA, 710FS, 730LM, 650AC, 681, 683 ( Neos Corporation ), </xnotran> U-120E (UNICHEM CO., LTD. Manufactured), and the like.
Further, the fluorine-based surfactant can also preferably use an acrylic compound having a molecular structure containing a functional group containing a fluorine atom, and the functional group containing a fluorine atom is partially cleaved when heat is applied, thereby volatilizing the fluorine atom. Examples of such fluorine-based surfactants include MEGAFACE DS series (chemical industry journal (2016, 2, 22 days) and Japanese Industrial News (2016, 2, 23 days)) manufactured by DIC Corporation, such as MEGAFACE DS-21.
Further, as the fluorine-based surfactant, a polymer of a fluorine atom-containing vinyl ether compound having a fluorinated alkyl group or a fluorinated alkylene ether group and a hydrophilic vinyl ether compound is also preferably used.
Further, as the fluorine-based surfactant, a terminal-capped polymer can also be used.
Further, as the fluorine-based surfactant, a fluorine-containing polymer compound containing a structural unit derived from a (meth) acrylate compound having a fluorine atom and a structural unit derived from a (meth) acrylate compound having 2 or more (preferably 5 or more) alkyleneoxy groups (preferably ethyleneoxy groups and propyleneoxy groups) can also be preferably used.
Further, as the fluorine-based surfactant, a fluorine-containing polymer having a group having an ethylenically unsaturated bond in a side chain can also be used. Examples thereof include MEGAFACE RS-101, RS-102, RS-718K and RS-72-K (manufactured by DIC Corporation).
From the viewpoint of improving environmental compatibility, preferred as the fluorine-based surfactant are surfactants derived from alternative materials to compounds having a linear perfluoroalkyl group having 7 or more carbon atoms, such as perfluorooctanoic acid (PFOA) and perfluorooctanesulfonic acid (PFOS).
Examples of the nonionic surfactant include glycerin, trimethylolpropane, trimethylolethane, and ethoxylates and propoxylates thereof (e.g., glycerin propoxylate, glycerin ethoxylate), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, and sorbitan fatty acid ester. Specific examples thereof include Pluronic L10, L31, L61, L62, 10R5, 17R2, 25R2, HYDROPALAT WE 3323 (manufactured by BASF Corporation), tetronic 304, 701, 704, 901, 904, 150R1 (manufactured by BASF Corporation), solsperse 20000 (manufactured by Lubrizol Limited), NCW-101, NCW-1001, NCW-1002 (manufactured by FUJIFILM Wako Pure Chemical Corporation), PI0NIN D-1105, D-6112-W, D-6315 (manufactured by Takemo Oil & Fat Co., ltd.), lfine E1010, surfynol 104, 400, 440 (manufactured by Nisin Co., ltd.), and the like.
Examples of the silicone surfactant include linear polymers composed of siloxane bonds and modified siloxane polymers having organic groups introduced into the side chains or the ends thereof.
Specific examples of Silicone surfactants include EXP.S-309-2, EXP.S-315, EXP.S-503-2, EXP.S-505-2 (manufactured by DIC Corporation), SIL 8032AD DITIVE, toray Silicone DC3PA, toray Silicone SH7PA, toray Silicone DC11PA, toray Silicone SH21PA, toray Silicone SH28PA, ay Silicone SH H29PA, toray Silicone SH30PA, ay Silicone SH8400 (manufactured by Dow Corning Toray Co., ltd.), X-22-52, X-22-4272, X-22-6266, KF-351A, K354L, KF-355A, KF-945, KF-640, 642, 643-643, X-22-4291, X-61341, KF-4915-60031, KP-60015, KP-60031, KP-125, KP-600104, KP-60031, KP-15 KP-600105, KP-600101-125, KP-600104, KP-600105, KP-600104, KP-301, KP-306, KP-310, KP-322, KP-323, KP-327, KP-341, KP-368, KP-369, KP-611, KP-620, KP-621, KP-626, KP-652 (manufactured by Shin-Etsu Silicone Co., ltd., above), F-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 (manufactured by Momentive Performance Materials Inc., above), BYK300, BYK306, BYK307, BYK310, cheK 320, BYK323, BYK325, BYK330, BYK313, BYK315N, BYK331, BYK333, BYK345, BYK347, BYK378, BYK349, BYK370, BYK377, BYK (manufactured by Mie, above), and the like.
One kind of surfactant may be used alone, or two or more kinds may be used.
When the photosensitive composition layer contains a surfactant, the content of the surfactant is preferably 0.01 to 3.0% by mass, more preferably 0.01 to 1.0% by mass, and still more preferably 0.05 to 0.80% by mass, based on the total mass of the photosensitive composition layer.
From the viewpoint of improving reliability and laminatability, the content of water in the photosensitive composition layer is preferably 0.01 to 1.0 mass%, more preferably 0.05 to 0.5 mass%, based on the total mass of the photosensitive composition layer.
The layer thickness (film thickness) of the photosensitive composition layer is generally 0.1 to 300. Mu.m, preferably 0.2 to 100. Mu.m, more preferably 0.5 to 50 μm, still more preferably 0.5 to 15 μm, particularly preferably 0.5 to 10 μm, most preferably 0.5 to 8 μm. This improves the developability of the photosensitive composition layer, and improves the resolution.
In one embodiment, the thickness is preferably 0.5 to 5 μm, more preferably 0.5 to 4 μm, and still more preferably 0.5 to 3 μm.
(impurities, etc.)
The photosensitive composition layer sometimes contains impurities.
Examples of the impurities include metal impurities or ions thereof, halide ions, residual organic solvents, and residual monomers.
Examples of the metal impurities include sodium, potassium, magnesium, calcium, iron, manganese, copper, aluminum, titanium, chromium, cobalt, nickel, zinc, tin, and ions and halide ions thereof.
Among them, from the viewpoint of easy contamination, sodium ions, potassium ions, and halide ions are preferably contained in the following amounts.
The metal impurities are compounds different from the particles (for example, metal oxide particles) that can be contained in the transfer film.
The content of the metal impurities is preferably 80 mass ppm or less, more preferably 10 mass ppm or less, and further preferably 2 mass ppm or less, with respect to the total mass of the photosensitive composition layer. The lower limit is preferably 1 mass ppb or more, more preferably 0.1 mass ppm or more.
Examples of the method for adjusting the content of the impurity include a method of selecting a raw material having a small content of the impurity as a raw material of the photosensitive composition layer, a method of preventing the impurity from being mixed in when the photosensitive composition layer is formed, and a method of cleaning and removing the impurity.
The content of the impurities can be quantified by a known method such as ICP emission spectrometry, atomic absorption spectrometry, or ion chromatography.
Examples of the residual organic solvent include benzene, formaldehyde, trichloroethylene, 1, 3-butadiene, carbon tetrachloride, chloroform, N-dimethylformamide, N-dimethylacetamide, and hexane.
The content of the residual organic solvent is preferably 100 mass ppm or less, more preferably 20 mass ppm or less, and further preferably 4 mass ppm or less, with respect to the total mass of the photosensitive composition layer. The lower limit is preferably 10 mass ppb or more, more preferably 100 mass ppb or more, with respect to the total mass of the photosensitive composition layer.
As a method for adjusting the content of the residual organic solvent, a method for adjusting drying conditions in a transfer film production method described later can be given. The content of the residual organic solvent can be quantified by a known method such as gas chromatography.
From the viewpoint of improving reliability and laminatability, the content of water in the photosensitive composition layer is preferably 0.01 to 1.0 mass%, more preferably 0.05 to 0.5 mass%, based on the total mass of the photosensitive composition layer.
[ intermediate layer ]
The transfer film preferably has an intermediate layer between the temporary support and the photosensitive composition layer.
Examples of the intermediate layer include a water-soluble resin layer and an oxygen barrier layer having an oxygen barrier function described as a "separation layer" in Japanese patent laid-open No. 5-072724.
The intermediate layer is preferably an oxygen barrier layer, and more preferably an oxygen barrier layer which exhibits low oxygen permeability and is dispersed or dissolved in water or an aqueous alkali solution (1 mass% aqueous solution of sodium carbonate at 22 ℃), from the viewpoint of improving productivity by improving sensitivity at the time of exposure and reducing the time load of the exposure machine.
Hereinafter, each component that the water-soluble resin layer (intermediate layer) can contain will be described.
The water-soluble resin layer (intermediate layer) contains a resin.
The resin preferably contains a water-soluble resin as a part or all thereof.
Examples of the resin that can be used as the water-soluble resin include resins such as polyvinyl alcohol resins, polyvinyl pyrrolidone resins, cellulose resins, acrylamide resins, polyethylene oxide resins, gelatin, vinyl ether resins, polyamide resins, and copolymers thereof.
Further, as the water-soluble resin, a copolymer of (meth) acrylic acid/vinyl compound, or the like can also be used. As the copolymer of (meth) acrylic acid/vinyl compound, a copolymer of (meth) acrylic acid/(meth) allyl acrylate is preferable, and a copolymer of methacrylic acid/allyl methacrylate is more preferable.
When the water-soluble resin is a copolymer of (meth) acrylic acid/vinyl compound, the composition ratio (% by mol) is, for example, preferably 90/10 to 20/80, more preferably 80/20 to 30/70.
The lower limit of the weight average molecular weight of the water-soluble resin is preferably 5000 or more, more preferably 7000 or more, and still more preferably 10000 or more. The upper limit value is preferably 200000 or less, more preferably 100000 or less, and still more preferably 50000 or less.
The dispersity (Mw/Mn) of the water-soluble resin is preferably 1 to 10, more preferably 1 to 5.
One kind of the water-soluble resin may be used alone, or two or more kinds thereof may be used.
The content of the water-soluble resin is not particularly limited, but is preferably 50 mass% or more, more preferably 70 mass% or more, further preferably 80 mass% or more, and particularly preferably 90 mass% or more, with respect to the total mass of the water-soluble resin layer (intermediate layer), from the viewpoint of further improving the oxygen barrier property and the interlayer mixing suppression ability. The upper limit is not particularly limited, but is preferably 99.9% by mass or less, and more preferably 99.8% by mass or less.
The intermediate layer may contain other components in addition to the above-described water-soluble resin.
As the other component, a polyhydric alcohol, an alkylene oxide adduct of a polyhydric alcohol, a phenol derivative, or an amide compound is preferable, and a polyhydric alcohol, a phenol derivative, or an amide compound is more preferable.
Further, as other components, for example, a known surfactant can be cited.
Examples of the polyhydric alcohols include glycerin, diglycerin, and diethylene glycol.
The number of hydroxyl groups in the polyhydric alcohol is preferably 2 to 10.
Examples of the alkylene oxide adduct of a polyol include compounds obtained by adding an ethyleneoxy group, a propyleneoxy group, or the like to the above polyol.
The average addition number of alkyleneoxy groups is preferably 1 to 100, more preferably 2 to 50, and further preferably 2 to 20.
Examples of the phenol derivative include bisphenol a and bisphenol S.
Examples of the amide compound include N-methylpyrrolidone.
The intermediate layer preferably contains at least one selected from the group consisting of water-soluble cellulose derivatives, polyols, oxide adducts of polyols, polyether resins, phenol derivatives, and amide compounds.
The molecular weight of the other component is preferably less than 5000, more preferably 4000 or less, still more preferably 3000 or less, particularly preferably 2000 or less, and most preferably 1500 or less. The lower limit is preferably 60 or more.
One or more of the other components may be used alone.
The content of the other component is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and further preferably 1% by mass or more, based on the total mass of the intermediate layer. The upper limit is preferably less than 30% by mass, more preferably 10% by mass or less, and further preferably 5% by mass or less.
The intermediate layer may contain impurities.
Examples of the impurities include impurities contained in the photosensitive composition layer.
The thickness of the water-soluble resin layer (intermediate layer) is not particularly limited, but is preferably 0.1 to 5 μm, more preferably 0.5 to 3 μm. When the thickness of the water-soluble resin layer (intermediate layer) is within the above range, the interlayer mixing suppression capability is excellent without lowering the oxygen barrier property. In addition, the increase in the time for removing the water-soluble resin layer (intermediate layer) during development can be further suppressed.
[ protective film ]
The transfer film may have a protective film on the photosensitive composition layer.
As the protective film, a resin film having heat resistance and solvent resistance can be used, and examples thereof include polyolefin films such as polypropylene films and polyethylene films, polyester films such as polyethylene terephthalate films, polycarbonate films, and polystyrene films.
As the protective film, a resin film made of the same material as the temporary support may be used.
Among them, as the protective film, a polyolefin film is preferable, a polypropylene film or a polyethylene film is more preferable, and a polyethylene film is further preferable.
The thickness of the protective film is preferably 1 to 100. Mu.m, more preferably 5 to 50 μm, still more preferably 5 to 40 μm, and particularly preferably 15 to 30 μm.
The thickness of the protective film is preferably 1 μm or more from the viewpoint of excellent mechanical strength, and preferably 100 μm or less from the viewpoint of relative low cost.
In the protective film, the number of fish eyes (fishery) having a diameter of 80 μm or more contained in the protective film is preferably 5/m 2 The following.
The term "fish eyes" refers to a phenomenon in which foreign matter, undissolved matter, oxidized and degraded matter, etc. of a material are taken into a film when the material is melted, kneaded, extruded, and the film is produced by a method such as biaxial stretching or casting.
The number of particles having a diameter of 3 μm or more contained in the protective film is preferably 30 particles/mm 2 Hereinafter, more preferably 10 pieces/mm 2 Hereinafter, more preferably 5 pieces/mm 2 The following.
This can suppress defects caused by transfer of the unevenness caused by the particles contained in the protective film to the photosensitive composition layer or the metal layer.
From the viewpoint of imparting winding properties, the surface of the protective film opposite to the surface in contact with the photosensitive composition layer preferably has an arithmetic average roughness Ra of 0.01 μm or more, more preferably 0.02 μm or more, and still more preferably 0.03 μm or more. On the other hand, it is preferably smaller than 0.50. Mu.m, more preferably 0.40 μm or smaller, and still more preferably 0.30 μm or smaller.
From the viewpoint of suppressing defects at the time of transfer, the surface roughness Ra of the surface of the protective film in contact with the photosensitive composition layer is preferably 0.01 μm or more, more preferably 0.02 μm or more, and still more preferably 0.03 μm or more. On the other hand, it is preferably less than 0.50. Mu.m, more preferably 0.40 μm or less, and further preferably 0.30 μm or less.
[ method for producing transfer film ]
The method for producing the transfer film is not particularly limited, and known methods can be used.
Examples of the method for producing the transfer film 10 include a method including the steps of: a step of applying the intermediate layer-forming composition to the surface of the temporary support 11 to form a coating film, and further drying the coating film to form the intermediate layer 13; and a step of applying a photosensitive composition to the surface of the intermediate layer 13 to form a coating film, and further drying the coating film to form the photosensitive composition layer 15.
When the transfer film 10 has the protective film 19, the protective film 19 may be pressure-bonded to the composition layer 17 of the transfer film 10 manufactured by the above-described manufacturing method.
As a method for producing the transfer film 10, it is preferable to produce the transfer film 10 including the temporary support 11, the intermediate layer 13, the photosensitive composition layer 15, and the protective film 19 by including a step of providing the protective film 19 so as to be in contact with a surface of the composition layer 17 on the side opposite to the temporary support 11 side.
After the transfer film 10 is manufactured by the above-described manufacturing method, the transfer film 10 can be wound to manufacture and store a roll-shaped transfer film. The transfer film 10 in the roll form can be supplied as it is to a step of bonding the substrate in a roll-to-roll manner, which will be described later.
The transfer film 10 may be produced by forming the composition layer 17 on the protective film 19.
(Water-soluble resin composition and method for Forming intermediate layer (Water-soluble resin layer))
The water-soluble resin composition preferably contains various components and solvents for forming the intermediate layer (water-soluble resin layer). In the water-soluble resin composition, the preferable range of the content of each component with respect to the total solid content of the composition is the same as the preferable range of the content of each component with respect to the total mass of the water-soluble resin layer.
The solvent is not particularly limited as long as it can dissolve or disperse the water-soluble resin, and is preferably at least one selected from water and water-miscible organic solvents, and more preferably water or a mixed solvent of water and water-miscible organic solvents.
Examples of the water-miscible organic solvent include alcohols having 1 to 3 carbon atoms, acetone, ethylene glycol and glycerol, preferably alcohols having 1 to 3 carbon atoms, and more preferably methanol or ethanol.
One solvent may be used alone, or two or more solvents may be used.
The content of the solvent is preferably 50 to 2500 parts by mass, more preferably 50 to 1900 parts by mass, and still more preferably 100 to 900 parts by mass, relative to 100 parts by mass of the total solid content of the composition.
The method for forming the water-soluble resin layer is not particularly limited as long as it is a method capable of forming a layer containing the above-mentioned components, and examples thereof include known coating methods (slit coating, spin coating, curtain coating, inkjet coating, and the like).
(photosensitive composition and method for Forming photosensitive composition layer)
From the viewpoint of excellent productivity, it is preferable to form the photosensitive layer by using a photosensitive composition containing components (for example, resin a, a polymerizable compound, a polymerization initiator, a thermal crosslinking agent, and the like) constituting the photosensitive composition layer and a solvent by a coating method.
Specifically, a method of forming a photosensitive composition layer by applying a photosensitive composition to an intermediate layer to form a coating film and drying the coating film at a predetermined temperature is preferable as a method of producing a transfer film.
The photosensitive composition preferably contains various components for forming the photosensitive composition layer and a solvent. In the photosensitive composition, the preferable range of the content of each component with respect to the total solid content of the composition is the same as the preferable range of the content of each component with respect to the total mass of the photosensitive composition layer.
The solvent is not particularly limited as long as it can dissolve or disperse each component other than the solvent, and a known solvent can be used. Specific examples thereof include alkylene glycol ether solvents, alkylene glycol ether acetate solvents, alcohol solvents (methanol, ethanol, and the like), ketone solvents (acetone, methyl ethyl ketone, and the like), aromatic hydrocarbon solvents (toluene, and the like), aprotic polar solvents (N, N-dimethylformamide, and the like), cyclic ether solvents (tetrahydrofuran, and the like), ester solvents (N-propyl acetate, and the like), amide solvents, lactone solvents, and mixed solvents containing two or more of these solvents.
The solvent preferably contains at least one selected from the group consisting of an alkylene glycol ether solvent and an alkylene glycol ether acetate solvent. Among these solvents, a mixed solvent containing at least one selected from the group consisting of an alkylene glycol ether solvent and an alkylene glycol ether acetate solvent and at least one selected from the group consisting of a ketone solvent and a cyclic ether solvent is more preferable, and a mixed solvent containing at least 3 of an alkylene glycol ether, an alkylene glycol ether acetate solvent, and a ketone solvent is even more preferable.
Examples of the alkylene glycol ether solvent include ethylene glycol monoalkyl ether, ethylene glycol dialkyl ether, propylene glycol monoalkyl ether (propylene glycol monomethyl ether acetate, etc.), propylene glycol dialkyl ether, diethylene glycol dialkyl ether, dipropylene glycol monoalkyl ether, and dipropylene glycol dialkyl ether.
Examples of the alkylene glycol ether acetate solvent include ethylene glycol monoalkyl ether acetate, propylene glycol monoalkyl ether acetate, diethylene glycol monoalkyl ether acetate, and dipropylene glycol monoalkyl ether acetate.
Examples of the ketone solvent include acetone, methyl ethyl ketone, methyl isobutyl ketone, 2-heptanone, and cyclohexanone.
As the solvent, a solvent described in paragraphs [0092] to [0094] of International publication No. 2018/179640 and a solvent described in paragraph [0014] of Japanese patent application laid-open No. 2018-177889 can be used, and these contents are incorporated in the present specification.
One solvent may be used alone, or two or more solvents may be used.
The content of the solvent is preferably 50 to 1900 parts by mass, more preferably 100 to 1200 parts by mass, and still more preferably 100 to 900 parts by mass, based on 100 parts by mass of the total solid content of the composition.
Examples of the method for applying the photosensitive composition include a printing method, a spray coating method, a roll coating method, a bar coating method, a curtain coating method, a spin coating method, and a die coating method (that is, a slit coating method).
The coating film of the photosensitive composition is preferably dried by heating or drying under reduced pressure.
The drying temperature is preferably 90 ℃ or higher, more preferably 100 ℃ or higher, and still more preferably 110 ℃ or higher. The upper limit is not particularly limited, but is preferably 130 ℃ or lower, more preferably 120 ℃ or lower.
The drying time is preferably 20 seconds or more, more preferably 40 seconds or more, and still more preferably 60 seconds or more. The upper limit is not particularly limited, but is preferably 450 seconds or less, and more preferably 300 seconds or less. The drying temperature is preferably 80 ℃ or higher, and more preferably 90 ℃ or higher. The upper limit thereof is preferably 130 ℃ or lower, more preferably 120 ℃ or lower. Drying can also be performed by continuously changing the temperature.
The drying time is preferably 20 seconds or more, more preferably 40 seconds or more, and still more preferably 60 seconds or more. The upper limit value is not particularly limited, but is preferably 600 seconds or less, and more preferably 300 seconds or less.
Further, the transfer film can be manufactured by bonding a protective film to the photosensitive composition layer.
The method for bonding the protective film to the photosensitive composition layer is not particularly limited, and known methods can be exemplified.
Examples of the means for bonding the protective film to the photosensitive composition layer include known laminators such as a vacuum laminator and an automatic cutting laminator.
The laminator is preferably provided with an optional heatable roller such as a rubber roller and can be pressurized and heated.
[ examples ]
The features of the present invention will be described in more detail below with reference to examples and comparative examples. The materials, the amounts used, the ratios, the contents of the treatment, the steps of the treatment, and the like shown in the following examples can be appropriately modified without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be construed as being limited to the specific examples shown below.
In the following examples, the weight average molecular weight of the resin was determined by polystyrene conversion based on Gel Permeation Chromatography (GPC). Also, the acid value used is the theoretical acid value.
< Material used for production of transfer film >
Materials (photosensitive composition and composition for forming an intermediate layer) used for producing the transfer film used in the examples will be described.
(Components of photosensitive composition)
The photosensitive composition layer of the transfer film is formed using the photosensitive composition.
The photosensitive compositions used in the examples and comparative examples were obtained by mixing the following components in the formulations shown in tables 2 to 3. The numerical values of the respective components in tables 2 to 3 are parts by mass.
In addition, in the preparation of the photosensitive composition, a mixed solvent containing methyl ethyl ketone (60 parts by mass manufactured by SANKYO CHEMICAL co., ltd.) and propylene glycol monomethyl ether acetate (40 parts by mass manufactured by SHOWA DENKO k.k.) was prepared, and the respective components were added to the mixed solvent in the formulations shown in the table shown later. The solid content concentration of each photosensitive composition was 13 mass%.
[ resin ]
Compounds 1 to 4: resins (compounds) respectively having the characteristics shown below
In addition, compounds 1 to 4 correspond to alkali-soluble resins.
[ Table 1]
In the above table, in the column of "composition", the kind of the structural unit contained in the resin is shown for each resin (compound), and the mass ratio of the content of each structural unit is shown in parentheses.
The name of the monomer from which each structural unit originates is shown as the type of each structural unit.
For example, compound 1 is a resin having a styrene-based structural unit, a methacrylic acid-based structural unit, and a methyl methacrylate-based structural unit, respectively, in a mass ratio of 32: 28: 40.
[ polymerizable Compound ]
BPE-500: ethoxylated bisphenol A dimethacrylate, shin-Nakamura Chemical Co., ltd
BPE-200: ethoxylated bisphenol A dimethacrylate, shin-Nakamura Chemical Co., ltd
BPE-100: ethoxylated bisphenol A dimethacrylate, shin-Nakamura Chemical Co., ltd
Polymerizable compound 1: dimethacrylate of polyethylene glycol having ethylene oxide of 15 mol and propylene oxide of 2 mol added to both ends of bisphenol A
M-270: ARONIX M-270, polypropylene glycol diacrylate (n. Apprxeq.12), TOAGOSEI co., ltd
A-TMPT: trimethylolpropane triacrylate, shin-Nakamura Chemical Co., ltd
SR454: ethoxylated (3) trimethylolpropane trimethacrylate, manufactured by Arkema S.A. Ltd
SR502: ethoxylated (9) trimethylolpropane trimethacrylate, manufactured by Arkema s.a
A-9300-CL1: caprolactone-modified tris- (2-acryloyloxyethyl) isocyanurate, shin-Nakamura Chemical Co., ltd
[ thermal crosslinking agent ]
SBB-70P: duranate, ASAHI KASEI CORPORATION, manufactures
TPA-B80E: duranate, ASAHI KASEI CORPORATION, manufactures
[ polymerization initiator ]
B-CIM:2,2' -bis (2-chlorophenyl) -4,4', 5' -tetraphenylbisimidazole (2- (2-chlorophenyl) -4, 5-diphenylimidazole dimer), KUROGANE KASEI Co., ltd
[ additives ]
SB-PI 701:4,4' -bis (diethylamino) benzophenone, sanyo writing Co., ltd
Colorless crystal violet: manufactured by Tokyo Chemical Industry Co., ltd
N-phenylglycine: manufactured by Tokyo Chemical Industry Co., ltd
Bright green: manufactured by Tokyo Chemical Industry Co., ltd
CBT-1: carboxy benzotriazole, joohoku CHEMICAL co
Mixture 1: 1:1 (mass ratio) mixture of 1- (2-di-n-butylaminomethyl) -5-carboxybenzotriazole and 1- (2-di-n-butylaminomethyl) -6-carboxybenzotriazole
Phenothiazine: manufactured by FUJIFILM Wako Pure Chemical Corporation
Irganox245: manufactured by BASF corporation
N-nitrosophenylhydroxylamine aluminium salt: manufactured by FUJIFILM Wako Pure Chemical Corporation
Phenidone (Tokyo Chemical Industry Co., ltd.; manufactured by Ltd.)
F-552: fluorine-based surfactant manufactured by DIC Corporation
(Components of the composition for Forming intermediate layer)
The following components were mixed to prepare a composition for forming an intermediate layer. The unit of the amount of each component is part by mass.
Ion exchange water: 38.12 parts by mass
Methanol (manufactured by Mitsubishi Gas Chemical Company, inc.): 57.17 parts by mass
KURARAY POVAL 4-88LA (polyvinyl alcohol, KURARAY co., ltd.): 3.22 parts by mass
Polyvinylpyrrolidone K-30 (NIPPON shokubali co., ltd.): 1.49 parts by mass of dEGAFACE F-444 (fluorine-based surfactant, manufactured by DIC Corporation): 0.0035 parts by mass
< preparation of transfer film >
Transfer films were produced in examples 1, 5 to 7 and comparative example 1 by the following procedure.
First, the photosensitive compositions of examples and comparative examples were applied onto a temporary support (polyethylene terephthalate film (lumicror 169440, toray ingredients, inc.) having a thickness of 16 μm and a haze of 0.6%) by a bar coater so that the thickness after drying became the thickness shown in tables 2 to 3, and dried at 80 ℃ by an oven to form a photosensitive composition layer (negative photosensitive composition layer).
A transfer film was prepared by pressure-bonding polyethylene terephthalate (169440, produced by TORAY INDUSTRIES, INC.) having a thickness of 16 μm as a protective film onto the obtained photosensitive composition layer.
In examples 2 to 4 and 8 to 10, transfer films were produced in the following manner.
First, an intermediate layer-forming composition was applied to a temporary support (a polyethylene terephthalate film (manufactured by lumiror 169sk 40, toray industries, inc.) having a thickness of 16 μm and a haze of 0.6%) by a bar coater so that the dried thickness became the thickness shown in tables 2 to 3, and the intermediate layer was formed by drying the composition at 90 ℃ in an oven.
Further, a photosensitive composition was applied onto the intermediate layer using a bar coater so that the thickness after drying became the thickness shown in tables 2 to 3, and dried at 80 ℃ using an oven to form a photosensitive composition layer (negative photosensitive composition layer).
A transfer film was prepared by pressure-bonding polyethylene terephthalate (169440, produced by TORAY INDUSTRIES, INC.) having a thickness of 16 μm as a protective film onto the obtained photosensitive composition layer.
< production of laminate >
A PET substrate with a copper layer was used, in which a copper layer having a thickness of 500nm was formed on a PET film (polyethylene terephthalate film) having a thickness of 200 μm by a sputtering method.
The transfer film thus produced was cut into a 10cm square, and the protective film was peeled off, and the film was laminated on the PET substrate with the copper layer under lamination conditions of a roll temperature of 90 ℃, a line pressure of 0.8MPa, and a line speed of 3.0m/min, so that the photosensitive composition layer was in contact with the copper layer on the surface of the PET substrate, to obtain a laminate.
At this point, when the transfer film does not include the intermediate layer, the laminate has a structure of "PET film-copper layer-photosensitive composition-temporary support", and when the transfer film includes the intermediate layer, the laminate has a structure of "PET film-copper layer-photosensitive composition-intermediate layer-temporary support".
Next, the temporary support was peeled off from the obtained laminate, and a photomask having a pattern with a line (μm)/space (μm) of 5/5 was brought into close contact with the exposed surface of the laminate. Using a high-pressure mercury lamp exposure machine (MAP-1200L, japan Science Engineering Co., ltd., main wavelength: 365 nm), an exposure amount of 50mJ/cm was applied 2 Light is irradiated. The exposure amount is the exposure amount of the line and space shape of the resist pattern reproduction photomask obtained after development.
Then, development was performed using a 1.0% sodium carbonate aqueous solution at 30 ℃ as a developer. Specifically, in the development, a 40-second shower treatment was performed, an air knife (AirKnife) treatment was performed to throw off the developer, and then a 30-second shower treatment was performed with pure water, and further an air knife treatment was performed.
Thus, a laminate having a resist pattern with a line-and-space shape was obtained.
Next, the laminate having the resist pattern was heated under the heating conditions ("heating temperature and heating time") described in tables 2 to 3 described later.
Then, the obtained laminate was immersed in a 10 mass% sulfuric acid aqueous solution (liquid temperature: 40 ℃ C.) for 3 minutes.
Next, the resulting laminate was placed in a Copper sulfate plating solution (Copper sulfate 75g/L, sulfuric acid 190g/L, chloride ion 50 ppm by mass, "coater Glyme PCM" manufactured by Meltex Inc., 5 mL/L) at a concentration of 1A/dm 2 Copper plating treatment was performed under the conditions of (1).
After the above-described laminate after the copper plating treatment was washed with water and dried, the laminate was immersed in a 1 mass% potassium hydroxide aqueous solution (pH = 13.5) at 50 ℃, whereby the resist pattern was peeled off.
The copper layer (seed layer) of the laminate after the resist pattern stripping step was removed with an aqueous solution containing 0.1 mass% sulfuric acid and 0.1 mass% hydrogen peroxide to obtain a copper wiring pattern. The copper wiring pattern was observed with an optical microscope, and the shape of the conductor pattern was evaluated according to the following criteria.
1: no conductor pattern is formed, or the shape of the formed conductor pattern is largely deformed.
2: the shape of the conductor pattern formed was approximately the desired shape, but distortion was observed in a part.
3: the conductor pattern is formed in a desired shape without deformation.
In tables 2 to 3, the columns "heating temperature and heating time" describe the temperature and time when the laminate having the resist pattern is heated, and for example, in example 1, the column "120 ℃ 20 minutes" indicates that the laminate is heated at 120 ℃ for 20 minutes.
In tables 2 to 3, the column "elastic modulus X (GPa)" shows the elastic modulus X (GPa), and the column "elastic modulus X/elastic modulus Y" shows the X/Y.
[ Table 2]
[ Table 3]
As shown in the table, according to the method of the present invention, it was confirmed that the desired effect was obtained.
Description of the symbols
10-transfer film, 11-temporary support, 13-intermediate layer, 15-photosensitive composition layer, 17-composition layer, 19-protective film.
Claims (19)
1. A method for manufacturing a laminate having a conductor pattern, comprising:
a bonding step of bonding a transfer film having a temporary support and a negative photosensitive composition layer to a substrate having a metal layer on a surface thereof so that the surface of the transfer film opposite to the temporary support is in contact with the metal layer of the substrate;
an exposure step of pattern-exposing the photosensitive composition layer;
a developing step of performing a developing treatment on the exposed photosensitive composition layer to form a resist pattern;
a heating step of heating the resist pattern;
a cleaning step of cleaning the heated resist pattern with an acidic solution;
a plating step of performing plating treatment on the metal layer located in a region where the resist pattern is not arranged;
a stripping step of stripping the resist pattern; and
a removing step of removing the metal layer exposed in the peeling step to form a conductor pattern on the substrate,
a temporary support stripping step of stripping the temporary support is further provided between the bonding step and the exposure step or between the exposure step and the development step,
the photosensitive composition layer contains a thermal crosslinking agent.
2. The method for producing a laminate having a conductor pattern according to claim 1,
the surface of the resist pattern heated in the heating step on the side opposite to the substrate side has an elastic modulus of 5.0GPa or more.
3. The method for producing a laminate having a conductor pattern according to claim 1 or 2,
the elastic modulus of the surface of the resist pattern heated in the heating step on the side opposite to the substrate side is set to be elastic modulus X,
when the elastic modulus of the resist pattern heated in the heating step is set to be Y,
satisfying that X/Y is less than or equal to 1.2.
4. The method for manufacturing a laminate having a conductor pattern according to claim 1 or 2,
the photosensitive composition layer contains a polymerizable compound and a polymerization initiator.
5. The method for producing a laminate having a conductor pattern according to claim 4,
the polymerizable compound has an alkylene oxide-modified bisphenol structure.
6. The method for manufacturing a laminate having a conductor pattern according to claim 1 or 2,
the thermal crosslinking agent comprises a blocked isocyanate compound.
7. The method for manufacturing a laminate having a conductor pattern according to claim 1 or 2,
the temporary support has a haze of 1.0% or less.
8. The method for manufacturing a laminate having a conductor pattern according to claim 1 or 2,
the thickness of the temporary support is 50 [ mu ] m or less.
9. The method for manufacturing a laminate having a conductor pattern according to claim 1 or 2,
the transfer film has an intermediate layer between the temporary support and the photosensitive composition layer.
10. The method for manufacturing a laminate having a conductor pattern according to claim 9,
the middle layer is a water-soluble resin layer.
11. The method for manufacturing a laminate having a conductor pattern according to claim 1 or 2,
the exposure step is a step of performing pattern exposure through a photomask.
12. The method for manufacturing a laminate having a conductor pattern according to claim 1 or 2,
the exposure step is a step of pattern-exposing the photosensitive composition layer through a lens using actinic rays onto which an image of a photomask is projected.
13. The method for producing a laminate having a conductor pattern according to claim 1 or 2,
the temporary support peeling step is provided between the bonding step and the exposure step,
the exposure step is a step of pattern-exposing the photosensitive composition layer by bringing the surface exposed by peeling off the temporary support into contact with a photomask.
14. A transfer film having a temporary support and a negative photosensitive composition layer, wherein,
the photosensitive composition layer contains a thermal crosslinking agent,
the temporary support has a haze of 1.0% or less.
15. The transfer film according to claim 14,
the thickness of the temporary support is 50 [ mu ] m or less.
16. The transfer film according to claim 14 or 15,
the photosensitive composition layer contains a polymerizable compound and a polymerization initiator.
17. The transfer film according to claim 16,
the polymerizable compound has an alkylene oxide-modified bisphenol structure.
18. The transfer film according to claim 14 or 15, which has an intermediate layer between the temporary support and the photosensitive composition layer.
19. The transfer film according to claim 18,
the middle layer is a water-soluble resin layer.
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| JP2021-141013 | 2021-08-31 | ||
| JP2021141013A JP2023034674A (en) | 2021-08-31 | 2021-08-31 | Method for manufacturing laminate having conductor pattern, transfer film |
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| CN115729045A true CN115729045A (en) | 2023-03-03 |
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| JP (1) | JP2023034674A (en) |
| KR (1) | KR20230032974A (en) |
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